Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 47 , Issue 6
Showing 1-50 articles out of 64 articles from the selected issue
  • Fumio Nozaki, Haruo Ohta
    1974 Volume 47 Issue 6 Pages 1307-1310
    Published: 1974
    Released: March 27, 2006
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    The dehydrogenation of 2-propanol over the ortho cadmium phosphate catalyst has been investigated by means of a conventional tubular-flow reactor operating at atmospheric pressure. The adequate temperature for the calcination of catalyst was about 400 °C. The reaction-rate data were approximately arranged by Eq. (3), using the Langmuir-type expression described in the text. The catalytic activity for dehydrogenation to acetone was completely poisoned by the addition of a small amount of CCl3COOH during the course of the reaction, whereas the activity for dehydration to propylene was greatly enhanced. The behavior of CH2ClCOOH and C6H5COOH as poisons was also investigated. C5H5N had no effect on the catalytic reaction. It has been concluded that the cadmium phosphate is to be characterized as a basic catalyst.
  • Chiaki Hirose
    1974 Volume 47 Issue 6 Pages 1311-1318
    Published: 1974
    Released: March 27, 2006
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    The rotational spectra of ten isotopic species of ethylene oxide, 12C2H416O, 12C13CH416O, 12C2H418O, 12C2H3D16O, cis- and trans-12C2H2D216O, 12C13CH2D216O, and 12C2H2D218O were observed. A least-squares fit including centrifugal distortion effect to the first order was made to derive the effective values of the A′, B′, C′, τ′aaaa, τ′bbbb, τ′cccc, and τ′aabb parameters and their correlation factors; τ′bbcc and τ′aacc were found to be insignificant. The rotational constants were used to determine the r0, rs, and rm structures. The structural parameters were derived as:
    & r_0(CC)=1.470±0.003, r_s(CC)=1.466±0.002, r_m(CC)=1.462±0.003,
    & r_0(CH)=1.085±0.004, r_s(CH)=1.085±0.001, r_m(CH)= 1.086±0.004,
    & r_0(CO)=1.434±0.002, r_s(CO)=1.431±0.001, r_m(CO)=1.428±0.002,
    & ∠_0HCH=116.28±0.69, ∠_SHGH=116.61±0.09, ∠_mHGH=116.92±0.69,
    θ0=22.34±0.46, θs=21.99±0.11, θm=21.63±0.48 in units of Å and degrees; θ represents the angle of the H2C plane to the CC bond. The indicated error limits are 2.5 times the variances.
  • Teikichi Sasaki
    1974 Volume 47 Issue 6 Pages 1319-1322
    Published: 1974
    Released: March 27, 2006
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    The yield of trapped hydrogen atoms, Ht, in gamma-irradiated sulfuric acid glass is remarkably increased by adding a small amount, 10−2 M, of metallic ions. The increase is followed with a slow decrease at the higher solute concentrations. The efficiency of the formation depends on the kind of cationic solute. The largest G(Ht) is observed in a system containing Co2+ ions; it amounts to 8.7. These findings can be explained by a mechanism in which not only mobile electrons produced by the initial ionic processes, but also excited states of the matrix molecule, contribute to the Ht formation. The excitation energy is transferred from the matrix molecule to the solute, which consequently undergoes ionization; the resulting electron causes the Ht formation. This mechanism seems to be supported by the observation that the yield of Ht increases with a decrease in the charge-transfer energy of the solute in the rigid matrix.
  • Noriko Iwasaki, Jo Tomooka, Koichi Toyoda
    1974 Volume 47 Issue 6 Pages 1323-1325
    Published: 1974
    Released: March 27, 2006
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    The IR and Raman spectra of bis(methylthio)mercury and methyl(methylthio)mercury were studied. Fundamental vibrations were assigned as follows: frequencies 698, 330, 530 and 174 cm−1 to C–S stretching, S–Hg stretching, C–Hg stretching and C–S–Hg bending vibrations, respectively. The fundamental vibrations were confirmed by normal coordinate analysis. The force constants of S–C and S–Hg stretching vibrations were estimated to be 2.16 and 1.5 md/Å, respectively.
  • Takako Amano, Yoshiya Kanda
    1974 Volume 47 Issue 6 Pages 1326-1330
    Published: 1974
    Released: March 27, 2006
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    The polarization of the charge-transfer phosphorescence has been studied by the method of photo-selection. It has been measured relative to the electric vector of the excitation light corresponding to the charge-transfer band in wavelength for the complexes of tetracyanobenzene, o-, m-, and p-dicyanobenzenes, tetrachlorophthalic anhydride, and phthalic anhydride as electron acceptors, and methyl-substituted benzenes as electron donors, in organic glass at 77 K. It has been shown that the degree of polarization through excitation into the charge-transfer band is almost constant in the phosphorescence region, while it gradually decreases as the ionization potential of the donor increases for any of the acceptors. These observations can reasonably be interpreted in terms of a model in which the charge-transfer phosphorescence is polarized normal to the molecular plane, irrespective of the complex, and in which the change in the polarization degree of the charge-transfer phosphorescence is responsible for the change in the direction of the transition moment of the charge-transfer absorption band.
  • Masae Kikuchi, Koichi Kikuchi, Hiroshi Kokubun
    1974 Volume 47 Issue 6 Pages 1331-1333
    Published: 1974
    Released: March 27, 2006
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    Rate constants for quenching of several triplets by ferrocene have been determined in ethanol. Most triplets have been found to be deactivated by ferrocene, yielding no observable transient absorption. The rate constant increases with increasing triplet energy in the range 8000–17000 cm−1. The quenching mechanism has been discussed, the lowest triplet level of ferrocene being estimated to be 15000±1000 cm−1.
  • Niro Matsuura, Kisaburo Umemoto
    1974 Volume 47 Issue 6 Pages 1334-1337
    Published: 1974
    Released: March 27, 2006
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    The solubility products of thallium halides were measured in dimethyl sulfoxide, N,N′-Dimethylformamide, and propylene carbonate for the purpose of obtaining the values of the medium effect for these electrolytes on transfer from water to these solvents. The medium effects for cations were estimated from the standard potentials of metal/ion couples obtained by the method of the corrected rubidium scale. The medium effects for halide ions were calculated from the medium effects for thallium halides and the thallium ion. A comparison of extrathermodynamic assumptions was made for the values of the medium effect for the silver ion as estimated by various methods ; the method of the corrected rubidium scale was found to give a reasonable result.
  • Hisashi Ueda
    1974 Volume 47 Issue 6 Pages 1338-1341
    Published: 1974
    Released: March 27, 2006
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    The formation of two aromatic hydrocarbon ions on the surface of Al2O3–MoO3 has already been postulated. The concentrations of these paramagnetic species were measured for various solvents by using DPPH single crystals as the reference standard. The formation of two different aromatic ions on the surface of Al2O3–MoO3 could also be confirmed by the solvent dependence. The intensity of microwave magnetic field H1 and the modulation width were considered in this measurement. Without solvent molecules such as benzene on the oxide surface, an ESR signal without cation hyperfine structure was almost exclusively observed. The intensities and intensity ratio between the two components of the ESR absorption at g=2.00, with and without hyperfine structure, change with solvent. The results indicated that solvent molecules, when adsorbed on the oxide surface, form a surface structure or a surface system which makes the charge transfer from the oxide surface to the solute hydrocarbon easier.
  • Shinji Takahashi
    1974 Volume 47 Issue 6 Pages 1342-1345
    Published: 1974
    Released: March 27, 2006
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    The diffusion coefficients of radioactive methane (CTH3) in argon and in mixtures of carbon dioxide with argon(0.719, 0.497, and 0.245 mol fractions of aigon) were measured at the temperatures of 25, 50, and 75°C in the 15∼250 atm pressure range. The measurements were made through a plug of porous bronze in the diffusion cell by using the radioactive tracer technique. The diffusion coefficient-density products, Dρ, for the CTH3–argon system increased slightly with the density in the region below 5 mol/1, and decreased slightly in the region above 5 mol/1. The Dρ for the CTH3–mixture systems decreased slightly with the density over the whole range studied here. The density dependence of Dρ-values at high densities could not be predicted by Enskog-Thorne’s theory.
  • Hayao Kobayashi
    1974 Volume 47 Issue 6 Pages 1346-1352
    Published: 1974
    Released: March 27, 2006
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    Crystals of acridinium-TCNQ(ARD(TCNQ)2) are triclinic, space group P\bar1 with a=3.841(2), b=13.018(6), c=18.370(12)Å, α=114.32(5), β=119.31(4), γ=90.57(7)° and Z=1. ARD and TCNQ, are separately stacked to form columns along the a axis. Each ARD column is surrounded by six TCNQ, columns. The orientation of ARD is disordered. Intermolecular distance between adjacent TCNQs is 3.246 Å and that between adjacent ARDs is 3.418 Å. The possibility of a Peierls distortion of TCNQ columns was discussed on the basis of the model of one-dimensional distorted lattice. Calculations of free energy show that alternation of intermolecular spacing disappears at Peierls transition temperature, Tp of about 200 K. For T>Tp, the one-dimensional band is not split (metallic), while it is split below Tp(semiconductive). The specific heat curve shows a peak at about 180 K and the heat of transition is calculated to be about 130 cal/mol.
  • Mitsuo Sato, Takao Kwan
    1974 Volume 47 Issue 6 Pages 1353-1357
    Published: 1974
    Released: March 27, 2006
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    The ESR spectra of vanadyl tetraphenylporphin (VOTPP) have been studied in a number of organic matrices, with special attention paid to the resolution of the nitrogen shf lines. The matrices were classified into three groups according to their effects on the resolutions of the vanadium hf lines and of the nitrogen shf lines. In the A-group matrices, the spectra of VOTPP displayed well-resolved hf lines, accompanied by shf splittings; in the B-group matrices, the spectra gave rise to well-resolved hf lines, but without shf splittings, and in the C-group matrices, the hf lines were resolved only poorly. It is suggested that a high dispersion of VOTPP molecules is required for the higher resolution of spectra.
  • Kazuie Kimura, Masashi Imamura
    1974 Volume 47 Issue 6 Pages 1358-1362
    Published: 1974
    Released: March 27, 2006
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    The ESR linewidths of semiquinone anions of xanthene dyes in alkaline protic solvents were studied as functions of the temperature and the viscosity. It was found that the linewidths of phloxine semiquinone, the ESR spectra of which show three hyperfine lines due to two equivalent protons, decrease with a decrease in the temperature or an increase in the viscosity of the solvents, and vary unimolecularly. Such a variation can not be explained either by a usual “chemical exchange” process between different states or by intramolecular motion. We propose that the linewidths may be due to the modulation of the hyperfine coupling constants of H atoms; the modulation results from the dissociation and/or distortion of the hydrogen bonds.
  • Noriyuki Sakamoto, Masafumi Yoshida, Shizuo Arichi
    1974 Volume 47 Issue 6 Pages 1363-1367
    Published: 1974
    Released: March 27, 2006
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    The light scattering of a poly(2-vinylpyridine) solution was measured under various conditions. In solvents such as methanol, ethanol, 2-propanol, 2-butanone, and pyridine, anomalous Zimm plots with an upward inflection at lower angles were observed. This anomaly was especially striking in methanol, in which the dissymmetry coefficient was frequently less than unity. Systematic investigations carried out with methanol as a solvent revealed that; (1) the anomaly does not depend appreciably on the concentration or tacticity of the polymer, the temperature, or the wavelength of the incident light; (2) the anomaly diminishes with an increase in the molecular weight of the polymer; (3) the anomaly disappears upon the addition of dry ammonia of 10−2 mol/1 or more in methanol, and (4) similar perturbed Zimm plots are realized by the addition of a trace amount of hydrochloric acid or sulfuric acid in a methanol solution of a higher-molecular-weight fraction which showed a normal Zimm plot in pure methanol. The anomaly can not be explained in terms of the effects of the optical anisotropy of the polymer segment, but the external interference arising from the non-random arrangement of the polymer in solution may contribute to it.
  • Makoto Kodama, Tsunetaka Sasaki
    1974 Volume 47 Issue 6 Pages 1368-1372
    Published: 1974
    Released: March 27, 2006
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    The well-known starch-iodine reaction was taken up to study the applicability of gel filtration to the problem of physical chemistry. Gel filtration by the frontal analysis was carried out, the following results being obtained. (1) Soluble starch- and amylose–iodine systems give elution volumes of iodine containing constituents (Vsi and Vai, respectively) distinctly smaller than that of iodine, which decrease with increasing concentration of iodine, C, and starch, approaching the elution volume of starch. This is a direct experimental evidence of starch–iodine complex formation. (2) An equation derived for Vsi vs. C and Vai vs. C relations holds satisfactorily. The concentration of free iodine in equilibrium with the complex is calculated by the equation. (3) Presence of iodide ion facilitates the complex formation, but its decomposition is instantaneous when it is isolated from free iodine. (4) Some iodide ions are found to be incorporated in the complex. (5) Amylopectin also forms a complex with iodine, but the amount of iodide incorporated is not large. (6) Potentiometric titration of starch with iodine exhibits a similar behavior to the gel filtration measurement.
  • Shigeru Yamashita
    1974 Volume 47 Issue 6 Pages 1373-1374
    Published: 1974
    Released: March 27, 2006
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    The mass spectra of methyl and ethyl radicals have been determined by the photolyses of methyl and ethyl iodide using a high intensity light beam and a collision-free photochemical reactor incorporated in the ion-source of a mass spectrometer. The parent ion peak was the most intense in the mass spectra of methyl and of ethyl radicals. Fair agreement was found between the present work and the result obtained by previous workers for pyrolytically produced methyl radicals.
  • Takahide Saito, Naomichi Iso, Haruo Mizuno
    1974 Volume 47 Issue 6 Pages 1375-1379
    Published: 1974
    Released: March 27, 2006
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    The dissociation-association properties of phycocyanin, isolated from the red algae, “Porphyra tenera,” have been investigated by sedimentation velocity measurements at pH 6.8 and 5.4 and at the ionic strengths of 0.1 and 0.2. The sedimentation coefficient data indicated that the predominant component in the phycocyanin solution was a trimer at pH 6.8 and a hexamer at pH 5.4. The concentration dependence of the sedimentation coefficient for various hypothetic systems of the dissociation-association equilibrium of phycocyanin was simulated by a computer model. It was reasonable to consider, from the simulation, that the dissociation-association system of phycocyanin was trimer\ ightleftharpoonsmonomer at pH 6.8 and hexamer\ ightleftharpoonsmonomer at pH 5.4. The dissociation constant was calculated for each system. The value of the dissociation constant was 0.15×10−4 (g/dl)2 at pH 6.8 and an ionic strength of 0.1; 0.13×10−4 (g/dl)2 at pH 6.8 and an ionic strength of 0.2; 0.5×10−13 (g/dl)5 at pH 5.4 and an ionic strength of 0.1 and 0.1×10−13 (g/dl)5 at pH 5.4 and an ionic strength of 0.2. The dissociation constants decrease with an increase in the ionic strength in solution.
  • Yuuzi Takahata, Robert G. Parr
    1974 Volume 47 Issue 6 Pages 1380-1386
    Published: 1974
    Released: March 27, 2006
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    Energy correlation diagrams for molecules of type AH2 are examined by three different methods: (1) the quantum-mechanical virial theorem, (2) the method of median partition, (3) the integral Hellmann-Feynman theorem. Nuclear-nuclear repulsions are included. The formula for the first method takes the form W=−Σti, where ti is an orbital kinetic energy. The theory is applied to H2O, CH2, and BeH2. Negative-kinetic-energies-versus-angle diagrams for these molecules are presented. The pattern of the diagrams is quite different from the usual Walsh diagram. With this resolution non-bonding electrons play a significant role in determining bond angles. In the second method the resolution of the total energy takes the form Wi[ei+Vn(i)], where ei is a median electronic energy and Vn(i) is a resolved nuclear repulsion energy calculated from an expression derived from ideas of population analysis. The energies-versus-angle diagram thus obtained for H2O is similar to the one obtained by the first method. For the third method, the integral Hellmann-Feynman formula for the electronic energy change on bending is written in terms of corresponding orbital contributions, ΔEliΔEl(i), and nuclear-nuclear repulsion is added in a resolved form. For H2O the ΔEl resemble Walsh diagrams closely, both with and without the nuclear-nuclear repulsion increments. Wave functions used throughout are LCAO-SCF functions built from medium-size Gaussian basis sets.
  • Nobuo Sagi, Yukio Yamamoto, Kenji Nagaoka, Setsuo Takamuku, Hiroshi Sa ...
    1974 Volume 47 Issue 6 Pages 1387-1392
    Published: 1974
    Released: March 27, 2006
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    The gas-phase radiolysis of a mixture of toluene or ethylbenzene and dimethylamine has been studied at room temperature as a function of the dimethylamine pressure in order to investigate the structure and reactivity of the C7H7+ ion. The structure of the C7H7+ ion which takes part in the subsequent ion-molecule reaction was suggested to be the benzyl type on the basis of the reaction products. The radiolyses of toluene-α-d3 and ethylbenzene-α-d2 in the presence and in the absence of dimethylamine have been investigated, and the following information has been obtained: (i) the C7H7+ ion formed from toluene and ethylbenzene mainly consists of the benzyl ion, retaining its original structure; (ii) two types of scrambling processes may be involved in the C7H7+ ion formation, one of which, especially important in the case of toluene, includes the ring expansion of the original molecular ion, while the other consists of repeated rapid isomerization between the benzyl ion and the tropylium ion. These results were compared with those of mass spectrometric studies, which indicate that an almost complete isotope scrambling occurs, hence supporting the symmetrical tropylium structure for the C7H7+ ion.
  • Kinya Iijima, Shuzo Shibata
    1974 Volume 47 Issue 6 Pages 1393-1395
    Published: 1974
    Released: March 27, 2006
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    The molecular structure of tungsten oxide tetrachloride was determined by the sector-microphotometer method of gas electron diffraction. The molecule was found to have a square-pyramidal structure, and the following molecular parameters were obtained by a least-squares method; rg(W–Cl)=2.281±0.003 Å, rg(W–O)=1.686±0.011 Å, and rg(Cl···Cl(s))=3.151±0.015 Å. The OWCl angle, 102.4±1.3°, is much larger than the corresponding angles found in other square-pyramidal molecules such as XeOF4 and IF5.
  • Hiroshi Yoshida, Junkichi Sohma, Tetsuo Warashina
    1974 Volume 47 Issue 6 Pages 1396-1399
    Published: 1974
    Released: March 27, 2006
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    EPR spectrum in emission mode at the low-field hyperfine lines was observed for 1,4-naphthosemiquinone radical formed by the steady-state photolysis of solution of corresponding quinone in ethanol flowing through the cavity. Observed behavior of this spectrum was analyzed by a phenomenological way. The results support the view that the anomalous electron spin polarization is generated in the radical formation process. The conclusion was compared with the results of intermittent photolysis.
  • Hirotsugu Shiraishi, Hajime Kadoi, Kenichi Hasegawa, Yoneho Tabata, Ke ...
    1974 Volume 47 Issue 6 Pages 1400-1403
    Published: 1974
    Released: March 27, 2006
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    An apparatus was constructed for ESR measurements during electron irradiation, and the behavior of transient radicals in the plastic crystals of cyclohexane (CyH) and 2,2,3,3-tetramethylbutane (TMB) was investigated. It was found from the experiment that cyclohexyl radical produced by irradiation of CyH decays with a rate constant of 2×10−8 exp (−7.9 kcal/RT) cm3/s. The rate constant is in good agreement with the results reported by Buben et al. On the other hand, radicals formed in irradiated TMB were assigned to be
    (Remark: Graphics omitted.)
    from the present results. It was shown from the results that the assignment made by Marx et al. before should be corrected to some extent. In the plastic crystals of CyH and TMB, it was suggested that the decay reactions of the observed radicals are controlled by the diffusional migration of the radicals. The analysis of radiolytic products of TMB was also made, and the results were compared with the results of ESR observation.
  • Michio Kimura, Takesi Nakajima, Shigeho Inaba, Hisao Yamamoto
    1974 Volume 47 Issue 6 Pages 1404-1408
    Published: 1974
    Released: March 27, 2006
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    The structure of the title crystal (C19H27N·HCl·H2O) has been determined by X-ray diffraction method. The racemate crystallizes in monoclinic, space group P21/c with a=14.30, b=15.74, c=7.79Å, β=98°58′ and Z=4. The reflection intensities were measured visually from equi-inclination integrating Weissenberg photographs taken with CuKx radiation. The structure was solved by the direct method of phase determination. The final R factor was 0.113. The molecules are linked in endless chains along c-axis by N+···Cl and Cl···H2O···Cl hydrogen bonds. Two piperidine rings in the molecule have the chair conformation. This product which shows analgesic activity has a new molecular structure having a four-ring system, part of which is a benzomorphan nucleus.
  • Fusao Takusagawa, Taiichi Higuchi, Akira Shimada, Chihiro Tamura, Yosh ...
    1974 Volume 47 Issue 6 Pages 1409-1413
    Published: 1974
    Released: March 27, 2006
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    The crystal structure of pyrazinic acid has been determined by X-ray diffraction method. The crystal is orthorhombic, space group Pna21, a=11.352, b=7.363, c=6.454Å, and Z=4. The structure was solved by inspecting the sharpened Patterson map. The final R value is 6.4% for all observed reflections. The molecule does not take a zwitter ion, but a neutral form. The dimensions of the pyrazine ring are close to those of pyrazine. Each molecule is joined, through the O–H···N hydrogen bond with distance of 2.669 Å, to two neighboring molecules forming the chain. These chains are linked by the weak C–H···O hydrogen bond to form the sheet parallel to the (0 0 1) plane. This hydrogen bonding scheme is quite similar to that of nicotinic acid. The hydrogen bonding type found in nicotinic acid is considered energetically favored more than that found in picolinic acid.
  • Akira Ohyoshi, Noriyuki Takebayashi, Yutaka Hiroshima, Kenichiro Yoshi ...
    1974 Volume 47 Issue 6 Pages 1414-1418
    Published: 1974
    Released: March 27, 2006
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    Studies have been made of the photochemistry of cis-dihalogenotetraammineruthenium(III) in aqueous solutions. For the cis-dichlorocomplex, no photochemical reaction has been observed by the irradiation of the visible light region. For cis-dibromo- and cis-diiodo-complexes, a simple aquation of halide ligand seems to occur in a solution with a pH lower than 2.5. The typical values of the quantum yields for the cis-[RuX2(NH3)4] ++H2O\xrightarrowhν cis-[RuX(OH2)(NH3)4]2+X reaction were 0.27×10−2 (382 nm light) and 0.82×10−2(408 nm light) for dibromo- and dichloro-complexes respectively. The quantum yield was dependent on the wavelength of light, but was independent of the concentrations of halide and hydrogen ions. The quantum yield seems to depend on the oxidizability of the ligand or on probability of the deactivation process in the primary excited state. In accounting for the low quantum yield, it seems most probable that the photoexcited complex species is converted to the ground state by non-radiative transitions.
  • Takafumi Kanazawa, Takao Umegaki, Y\={o}z\={o} Kitajima, Takeshi Ogawa
    1974 Volume 47 Issue 6 Pages 1419-1421
    Published: 1974
    Released: March 27, 2006
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    Dissolution of the highpolyphosphate coacervates of magnesium, calcium and aluminum was studied in order to understand the conformational feature of polyphosphate chains in the coacervates. Electrical conductivity and viscosity of the coacervate solutions were measured. Paper chromatographic technique was employed for the analysis of the solutions. It was concluded that the polyphosphates dissolve into acid solvents without cleavage of phosphate chains, the degree in the extension of the chains being considerably small. Dissolution processes of the three coacervates were compared. Optimum conditions on the syntheses of the threadforming coacervates are given.
  • Goro Wada, Kyoko Tamaki
    1974 Volume 47 Issue 6 Pages 1422-1425
    Published: 1974
    Released: March 27, 2006
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    The kinetics of the electron transfer reaction between Tl(I) and Tl(III) was investigated in the presence of Ce(IV) by use of a radioactive tracer 204Tl. The apparent rate constant of the reaction, kapp, was dependent upon [H+] and [Co(IV)] (<0.6×103 M) and can be expressed by
    k_app=k_A+\frack_B[H^+]+\left(k_C+\frack_D[H^+]\ ight)[Ce(IV)].
    kapp is gradually saturated to a limiting value according to [H+] at higher [Ce(IV)]. The observed values are kA=4.70 M−1 h−1, kB=2.13 h−1, kC=1.30×103 M−2 h−1 and kD=2.61×103 M−1 h−1 at 50 °C. Since Ce(IV) is a one-electron-oxidant, Tl(I) is oxidized by one-electron transfer to produce Tl(II) as an intermediate. However, in the absence of one-electron-oxidant or -reductant, two electrons are transferred from Tl(I) to Tl(III) not through double steps of one-electron transfer but predominantly through a single step of two-electron transfer.
  • Hiroshi Ogino, Masatake Takahashi, Nobuyuki Tanaka
    1974 Volume 47 Issue 6 Pages 1426-1429
    Published: 1974
    Released: March 27, 2006
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    Kinetic studies of the reactions of the ferricyanide ion with cobalt(II)-aminopolycarboxylate complexes were carried out. The aminopolycarboxylates used in this study were trimethylenediaminetetraacetate (TRDTA), trans-1,2-cyclohexanediaminetetraacetate (CyDTA), propylenediaminetetraacetate(PDTA), and N-hydroxyethyl ethylenediaminetriacetate(HEDTA). The first step in the reaction is the rapid formation of a binuclear complex intermediate, [(ammopolycarboxylate)CoIIINCFeII(CN)5]n(n=5 for TRDTA, CyDTA and PDTA and 4 for HEDTA), followed by the dissociation of the intermediate to ferrocyanide and Co(III)-aminopolycarboxylate ions. The equilibrium constant of the formation reaction and the rate constant of the dissociation reaction of the intermediate at an ionic strength of 0.66 were 6.2×102 M−1 and 2.0×10−2 s−1 respectively for the TRDTA system at 5 °C, 3.3×10 M−1 and 2.7×10−2 s−1 for the CyDTA system at 25 °C, and 2.4×103 M−1 and 3.0×10−3 s−1 for the PDTA system at 25 °C. The rate constant of the dissociation of [hedta CoIIINCFeII(CN)5]4− was found to be smaller than 1×10−4 s−1 at 25 °C and at an ionic strength of 0.66.
  • Mutsuo Kodama
    1974 Volume 47 Issue 6 Pages 1430-1433
    Published: 1974
    Released: March 27, 2006
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    The kinetics of the substitution reactions of CyDTA with zinc(II)–EDMA and –EDDA complexes and that of EDTA with the nickel(II)-EDDA complex were studied systematically by using the polarographic technique. All the substitution reactions were found to be first-order with respect to the CyDTA or EDTA anion and also first-order with respect to the 1 : 1-ratio EDMA or EDDA complex. From a comparison of the observed rate constants with those estimated on the basis of the proposed reaction intermediates, the detailed reaction mechanisms were discussed. The rates of the reactions of zinc(II)–EDMA complex and nickel(II)–EDDA complex could be understood in terms of the ethylenediamine reaction mechanism, but that of the reaction of the zinc(II)–EDDA complex with the CyDTA anion could not. This discrepancy may be ascribed by the steric hindrance of the CyDTA anion to the formation of an ethylenediamine reaction intermediate in the reaction of the zinc(II)–EDDA complex.
  • Mutsuo Kodama
    1974 Volume 47 Issue 6 Pages 1434-1436
    Published: 1974
    Released: March 27, 2006
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    Zinc(II)–EDDA and –Trien complexes produced kinetic waves. By conducting a systematic examination of the nature of the kinetic waves, the reaction mechanisms and the rates of the rate-determining step were determined. The kinetic wave of the zinc(II)–EDDA complex could be ascribed to the reduction of the zinc(II) aquo ion formed upon its slow dissociation at the electrode surface. From a comparison of the observed rate constant with that estimated on the basis of the proposed reaction intermediate, the dissociation of the zinc(II)–EDDA complex was found to proceed through a reaction intermediate in which the leaving EDDA anion is bonded to the zinc(II) ion through the ethylenediamine chelate ring. In the case of the Trien complex, the kinetic wave could be ascirbed to the reduction of the zinc(II)–Trien complex formed upon the slow configurational change of the tetrahedral zinc(II)–Trien complex at the electrode surface.
  • Hiroji Aiba, Akira Yokoyama, Hisashi Tanaka
    1974 Volume 47 Issue 6 Pages 1437-1441
    Published: 1974
    Released: March 27, 2006
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    The complex formation of glycyl-L-histidine, glycyl-L-histidylglycine, and glycylglycyl-L-histidine with copper (II) ion in aqueous solutions containing equimolar amounts of copper(II) and the respective ligand was investigated by potentiometric and visible spectrophotometric methods. The presence of the following copper (II) complex species was assumed: CuLH2+, CuX, and CunYnn for glycyl-L-histidine-copper(II) and glycyl-L-histidylglycine–copper(II) systems, and CuLH2+, CuY, and CuZ2− for glycylglycyl-L-histidine-copper(II) system, where LH is the neutral species of the ligand and LH=XH2=YH3=ZH4. The formation and ionization constants were obtained graphically, and the distribution of copper(II) among the complex species was calculated for each system. The results indicate that copper(II) ions are bound to the imidazole and carboxyl (or carbonyl) groups in CuLH2+ and to the amino, imidazole, and deprotonated amide groups in CuX, CuY, and CuZ2−. The spectral blue shift accompanying a deprotonation in the region from a=4 to 5 in the glycyl-L-histidine and glycyl-L-histidylglycine copper(II) systems indicates the formation of a polymer complex CunYnn in which the imidazole ring acts as a bridge to connect copper atoms, where a represents moles of KOH added per completely protonated ligand.
  • Fumikazu Yajima, Yasuo Koike, Akira Yamasaki, Shizuo Fujiwara
    1974 Volume 47 Issue 6 Pages 1442-1446
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The cobalt-59 chemical shifts and line widths for about seventy cobalt(III) complexes of the [CoIII(en)x(NH3)6−2xyLy] (L= Cl, Br, NO2, N3, OH, H2O, CO3, and C2O4) type have been measured. The cobalt-59 chemical shifts of this type of complex are approximately represented by a simple relation:
    δ(ppm)=360x+\oversety\underseti=1∑δ_i(L) (x=0, 1, and 2),
    where δi(L) is the i-th ligand shift parameter which represents the contribution of the i-th ligand, L, to the total chemical shift. Three empirical rules can be derived from experimental observations: I. The chemical shift of a trans-isomer is higher than that of the corresponding cis-isomer. II. The line width of the trans-CoA4B2 isomer is larger than that of the cis-CoA4B2 isomer. III. The line width of a meridional isomer is larger than that of the corresponding facial isomer. Illustrative examples are presented where cobalt-59 NMR is used to identify cobalt (III) complexes and to study the kinetics and equilibrium in solution.
  • Masao Sekizaki
    1974 Volume 47 Issue 6 Pages 1447-1450
    Published: 1974
    Released: March 27, 2006
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    Bis(iminodiacetamide)copper(II) perchlorate was newly synthesized, and the crystal structure was determined from three-dimensional X-ray data collected on a diffractometer. The structure was refined by blockdiagonal least-squares methods to give R=0.08 for the 950 observed reflections. The crystals are monoclinic with the space group of P21/c. There are two formula units per unit cell with a=6.183, b=17.617, c=8.900 Å, and β=110.2°. The complex is centrosymmetric, in which the two ligand molecules coordinate to the central copper atom through two imino nitrogen atoms and two of the four amide oxygen atoms in trans positions, exhibiting a square-planar coordination. The other two amide oxygen atoms are weakly bonded to the copper atom above and below this square-plane, thus completing an s-facial distorted (elongated) octahedral coordination. The complex cations are held together through hydrogen bonds to form infinite chains along the a axis. These chains are connected with one another by perchlorate ions through hydrogen bonds, thus forming three-dimensional networks.
  • Mitsuo Higuchi, Kenji Takeshita, Ryoichi Senju
    1974 Volume 47 Issue 6 Pages 1451-1454
    Published: 1974
    Released: March 27, 2006
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    The reactions of N-chlorocarbamoylethyl starch with simple monoamines were investigated in order to elucidate the mechanism of the reaction of an isocyanate group with amines in an aqueous alkaline medium. It was confirmed that the N-chloroamide group reacts with amines through the formation of an isocyanate group. The reactions of the isocyanate with amines in the presence of sodium hydroxide obeyed the following equation: (rate of isocyanate–amine reaction)/(rate of isocyanate–OH reaction)=ku[amine]/ka[OH] showing no catalytic effects of reactants or products. The reactivities of most of the primary amino groups attached to primary carbon with the isocyanate are comparable to that of the hydroxide ion. The relative rates of the reactions of amines with the isocyanate are not always correlated to their basicities, even when differences in steric hindrance are not great. Both the enthalpy and entropy of activation for the isocyanate–amine reactions are smaller than those for the isocyanate–OH reaction.
  • Iwao Tabushi, Yoshinao Tamaru, Zen-ichi Yoshida
    1974 Volume 47 Issue 6 Pages 1455-1459
    Published: 1974
    Released: March 27, 2006
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    Forming a marked contrast to hydrolysis, the first-order rate constant in the acetolyses of 3-chloropropene sulfide (I) and 2-chloroethyl methyl sulfide (II) has been observed to be seriously decreased; this may be ascribed to the return to the starting material of the sulfonium intermediate (III′ or IV) by the chloride ion liberated in the course of the reaction. The reaction has substantially obeyed first-order kinetics, giving exclusively and quantitatively skeletally-rearranged 3-acetoxy-thietane (the first-order rate constant; k1=2.1×10−5 s−1, at 55.0 °C) and 2-acetoxyethyl methyl sulfide (k1=4.8×10−4 s−1, at 55.0 °C) from I and II respectively.
  • Ryoji Noyori, Masao Katô
    1974 Volume 47 Issue 6 Pages 1460-1466
    Published: 1974
    Released: March 27, 2006
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    The photo-induced reaction of cyclic α,β-unsaturated ketones with protic media is described. The irradiation of 2-cycloheptenone or 2-cyclooctenone in various protic solvents (alcohols, acetic acid, water, and diethylamine) results in the formation of Michael-type solvent adducts. The chemically-reactive species have been demonstrated to be the highly strained trans isomers in a ground state. The irradiation of cis-2-cyclononenone affords the stable trans isomer, which reacts in the dark with methyl alcohol at an elevated temperature to give 3-methoxycyclononanone. The irradiation of 2-cyclohexenone in methyl alcohol yields 3-methoxycyclohexanone in a poor yield. The possible existence of trans-2-cyclohexenone is discussed.
  • Akira Ishigaki, Toshiyuki Shono
    1974 Volume 47 Issue 6 Pages 1467-1470
    Published: 1974
    Released: March 27, 2006
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    The treatment of 2-methylfuran with phosphoric acid yields the 2,4,4-tris(5′-methyl-2′-furyl)-1-pentanol (1) as a tetrameric product. This product gives its acetate (2) on acetylation with acetic anhydride, and forms a equimolar adduct (3) after treatment with maleic anhydride. The structural formula of 1 is supported by the IR, UV, NMR, and mass spectral data and by the other experimental facts. The other oligomers are separated as a product (4) which contains tetra-, penta-, hexa-, and heptamer. The structure of these oligomers discussed, and some possible reaction mechanisms for oligomerization are suggested.
  • Tetsuo Nozoe, Toyonobu Asao, Hiroshi Susumago, Masayoshi Ando
    1974 Volume 47 Issue 6 Pages 1471-1476
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The Diazotization of 2-amino-6-bromo (or alkoxy)-azulene, with alkoxycarbonyl or cyano groups at the 1 and 3-positions, by sodium nitrite in dioxane–sulfuric acid afforded mainly the corresponding 2-diazo-2,6-azulenoquinone derivatives (2a, 2b, 16). The catalytic hydrogenation of these compounds gave 1,3-disubstituted 6-hydroxyazulenes (4a, 4b, 18), from which 1,3-disubstituted 6-alkoxy- or 6-acetoxy-azulenes were obtained. The diazotization of diethyl 2-amino-6-bromoazulene-1,3-dicarboxylate (1a) in dry benzene with isoamyl nitrite in the presence of hydrogen chloride afforded the 2,6-dichloroazulene derivative (20) and the 5-bromo-2-diazo-2,6-azulenoquinone derivative (21); the latter, accompanied by a bromine addition product (22), was also obtained by the bromination of 2a. The diazotization of diethyl 2-aminoazulene-1,3-dicarboxylate (25) afforded 2a and a deamination product (26). The structure and mechanism of the formation of these diazoazulenoquinones are discussed.
  • Kunisuke Izawa, Tadashi Okuyama, Takayuki Fueno
    1974 Volume 47 Issue 6 Pages 1477-1479
    Published: 1974
    Released: March 27, 2006
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    Hydrochlorination of cis- and trans-1 -phenylpropenes and their ring-substituted derivatives (p-CH3O, p-CH3, and p-Cl) has been studied in acetic acid at 16–35°C. 1-Phenylpropene gave predominantly a cis-adduct while the p-CH3O derivative yielded a non-stereospecific product. For the p-CH3O and p-CH3 derivatives, the cis isomer was found to be more reactive than the corresponding trans isomer, while for the p-Cl derivative the opposite relative reactivity was observed. The origins of these cis/trans reactivities have been discussed in terms of the electronic and steric effects on stability of the solvated transition state.
  • Kunisuke Izawa, Tadashi Okuyama, Takayuki Fueno
    1974 Volume 47 Issue 6 Pages 1480-1483
    Published: 1974
    Released: March 27, 2006
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    Kinetic investigations were carried out on the addition of 2,4-dinitrobenzenesulfenyl chloride to the geometrically isomeric pairs of various 1-arylpropenes as well as some related olefins. All the trans isomers of 1-arylpropenes were more reactive than the corresponding cis isomers and the Hammett correlations were observed for respective isomers with ρ=−2.64 (trans) and −2.3 (cis). By contrast, cis-alkenes were more than 10 times as reactive as the corresponding trans isomers. The reactivities of various unsaturated compounds in this reaction were found to be correlated with their ionization potentials constituting two lines accodring to the type of substrates. It was concluded that the greater reactivity of trans-1-arylpropene as compared with the cis isomer is ascribable to the difference in the charge-transfer interaction between the electrophile and a substrate at the transition state. The conclusion is contrasting to the generalization that the relative cis/trans reactivity of alkenes is determined mainly by the Coulombic interaction at the transition state.
  • Katsuaki Hagio, Naoto Yoneda
    1974 Volume 47 Issue 6 Pages 1484-1489
    Published: 1974
    Released: March 27, 2006
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    The reactions of 4-benzylthio-5-benzylthiomethyl-3-hydroxy-2-oxo-2,5-dihydrofuran with ammonia and primary amines gave 3-amino-4-benzylthio-5-benzylthiomethyl-3-pyrrolin-2-one derivatives. 3-Acylamino-4-benzylthio-5-benzylthiomethylene-3-pyrrolin-2-one derivatives, including the intermediate of the synthesis of holomycin by Büchi, were prepared by the treatment of the 3-acylaminolactams derived from the 3-aminolactams with chloranil or DDQ. Thiolutin and aureothricin were also synthesized from 3-acetamido- and 3-propionamido-4-benzylthio-5-benzylthiomethylene-1-methyl-3-pyrrolin-2-one respectively.
  • Akira Matsumoto, Joung Hee Lee, Masayuki Yoshida, Osamu Simamura
    1974 Volume 47 Issue 6 Pages 1490-1492
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The polarographic reduction potentials of aryl-substituted 1,2,4,5-tetra-aza- and 1,2,3,4,5,6-hexa-aza-pen-talenes were shown to be approximately governed by the numbers of nitrogen atoms and aryl-substituents. Such effect of nitrogen atoms was discussed in terms of the orbital energies of parent azapentalenes obtained by HMO calculations.
  • Akira Matsumoto, Masayuki Yoshida, Osamu Simamura
    1974 Volume 47 Issue 6 Pages 1493-1495
    Published: 1974
    Released: March 27, 2006
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    The title compounds have been synthesized, and their chemical reactivities and spectroscopic properties are discussed in comparison with those of 2,5-diphenyl-v-triazolo[4,5-d]-v-triazole.
  • Tadashi Sugawara, Hiizu Iwamura, Michinori Oki
    1974 Volume 47 Issue 6 Pages 1496-1499
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Thiane, 1,3-dithiane, and 1,3,5-trithiane were treated with t-butyl peroxybenzoate in the presence of cuprous chloride to yield benzoyloxylated products. Methylenes placed between two sulfur atoms were found to be more reactive than those next to one sulfur atom. Introduction of two benzoyloxy groups into 1,3,5-trithiane afforded cis-2,4-dibenzoyloxy-1,3,5-trithiane only. PMR spectra of benzoyloxylated products at various temperatures indicate that benzoyloxy-axial conformation is overwhelming for all the compounds investigated.
  • Sotaro Miyano, Harukichi Hashimoto
    1974 Volume 47 Issue 6 Pages 1500-1503
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The iodocyclopropanation of olefins by the iodocarbenoid of zinc generated from diethylzinc and iodoform was investigated. When the reaction was carried out in a neat olefin, cyclohexene, 1-hexene, cis-2-butene, isobutene, and styrene gave the corresponding iodocyclopropanes in yields of 70, 34, 63, 55, and 44% respectively, showing that the CHI3–Et2Zn system is a convenient route for iodocyclopropanes. The reaction with cyclohexene was investigated in some detail. syn-7-Iodonorcarane easily gave 3-ethylcycloheptene upon treatment with diethyl zinc in the presence of zinc iodide.
  • Michio Kobayashi, Eri Akiyama, Hiroshi Minato, Noboru Kito
    1974 Volume 47 Issue 6 Pages 1504-1508
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Arylazo p-tolyl sulfones(I) were thermolyzed or photolyzed in the presence of trapping agents such as α,N-diphenyl nitrone(II), α-phenyl N-t-butyl nitrone(III) and 2-methyl-2-nitrosopropane(X). ESR studies showed that phenyl radical or p-methoxy phenyl radical is produced from the decomposition of I and adds to II or III. The adduct of phenyl radical to II and that of p-methoxyphenyl radiacl to III were synthesized for comparison by separate pathways. The photolysis of phenyl p-tolylazo sulfone(Ia) in the presence of III yielded benzhydryl t-butyl nitroxide, benzoyl t-butyl nitroxide and t-butyl p-toluenesulfonyl nitroxide(XVI) radicals. The photolysis of la in the presence of X gave di-t-butyl nitroxide(XII) and XVI. The photolysis of phenylazotriphenylmethane in the presence of X yielded XII and t-butyl nitroxide radical. The mechanisms of the formation of these radicals are discussed. The formation of arenesulfonyl radicals from the decomposition of I has been proved indirectly (analyses of the products of the combination of nitroxide radicals with arenesulfonyl radicals) and directly (detection of t-butyl p-toluenesulfonyl nitroxide radical.
  • Toyoki Kunitake, Yoshio Okahata, Reiko Ando
    1974 Volume 47 Issue 6 Pages 1509-1515
    Published: 1974
    Released: March 27, 2006
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    Water-soluble copolymers containing protected hydroxamate groups were prepared by radical copolymerization of acetyl N-phenylacrylohydroxamate and acrylamide, and the hydroxamic acid group (PHA) was unmasked by treating it with hydroxylamine. In acetylation with p-nitrophenyl acetate (1.4 v/v% CH3CN–H2O, 30 °C) the PHA unit was less reactive than the corresponding monomeric compound. When the PHA content was low (3 mol%), the reactivity of a given PHA anion (true reacting species) was invariant (9.1 M−1 S−1) over a wide range of the dissociation of the PHA unit. However, in the case of the copolymer of a higher PHA content (11 mol%) the reactivity decreased as the neutralization of the PHA anion progressed. This phenomenon was attributed to the intramolecular aggregation of the undissociated PHA side chain. The deacylation rate of the acetylated PHA unit was comparable to those of the monomeric counterparts, in contrast with the acylation process. Finally, the probable role of the PHA unit as catalyst for the ester hydrolysis was discussed.
  • Michiharu Kato, Fusao Kido, Ming-Der Wu, Akira Yoshikoshi
    1974 Volume 47 Issue 6 Pages 1516-1521
    Published: 1974
    Released: March 27, 2006
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    An efficient route based upon solvolytic fragmentation of a cyclopentadiene-dichloroketene adduct 4c has been investigated for the synthesis of trimethoxyphenylpropyltropolone 2b, a synthetic intermediate of colchicine 1a. Attempted synthesis of the corresponding unsaturated tropolones 8a and 10 is also discussed.
  • Tadahiro Wakui, Yoshio Otsuji, Eiji Imoto
    1974 Volume 47 Issue 6 Pages 1522-1526
    Published: 1974
    Released: March 27, 2006
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    The reactions of 2-bromo-2-methyldimedone (1), 2,2-dibromodimedone (6), 2-bromo- and 2-chloro-2-methylcyclohexane-1,3-dione (10a and 10b) and 2-acetyl-2,6-dibromocyclohexanone (14) with an equivalent of sodium acetate in a variety of solvents were studied. The constitutions and proportions of the products obtained by these reactions depended strongly on the structure of 2-halogeno-1,3-diketones and the solvents employed. The results were discussed in terms of the mechanisms proposed.
  • Mutsukazu Kamo, Hisao Kanda, Yoichiro Sato, Nobuo Setaka
    1974 Volume 47 Issue 6 Pages 1527-1529
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Pitch prepared by heating polyvinyl chloride at 400 °C (PVC pitch) was fractionated by vacuum sublimation. The fractions were studied by means of elementary analysis, determination of molecular weight, IR spectroscopy and NMR spectroscopy. It was found that each fraction has a characteristic constituent as follows: 1) Zones 1 and 2 are composed of some aromatic nuclei with 3–4 rings and 3–5 rings linked with aliphatic chains, respectively; 2) Zones 3 and 4 are composed of condensed aromatic nuclei with 6–8 rings and 6–7 rings, respectively; 3) In zone 5, aromatic nuclei have 2–4 aromatic rings on an average, and the ratio of the aliphatic group is higher than that of other zones; 4) The sublimation residue is mainly composed of condensed aromatic nuclei, and the ratio of aromatic hydrogen to aliphatic hydrogen in the residue is the highest.
  • Satoru Kumazawa, Koichi Nishihara, Tadahiro Kato, Yoshio Kitahara, His ...
    1974 Volume 47 Issue 6 Pages 1530
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Sesquirosefuran (I) was synthesized by the coupling of geranyl bromide with 2,2′-bis(3-methylfuryl)-mercury in 29% yield.
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