Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 51 , Issue 1
Showing 1-50 articles out of 80 articles from the selected issue
  • Tsutomu Minato, Shinichi Yamabe, Hiroshi Fujimoto, Kenichi Fukui
    1978 Volume 51 Issue 1 Pages 1-10
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The reaction path of radical-radical recombination and disproportionation has been studied by means of a perturbational method with a clear orbital interaction concept, and the mechanism of these reactions has been elucidated theoretically. It has been confirmed that these termination reactions do not have a common transition state. The recombination is found to take the path which gives the maximum interaction between the singly occupied molecular orbitals (SOMO’s) of two radical species, whereas the disproportionation is shown to take the route which gives the significant charge transfer interaction from the particular doubly occupied (DO) MO of one radical to the SOMO of the other radical. The DOMO localized at the C–H bond donates electrons to the SOMO to cause the hydrogen abstraction. In the process of disproportionation, one radical which abstracts a hydrogen atom acts as an electron-acceptor and the other radical with the hydrogen atom to be abstracted as an electron-donor. The difference between the mechanism of the recombination and that of the disproportionation is clarified in terms of the mode of the orbital interaction.
  • Osamu Kikuchi, Akihisa Hiyama, Hiroshi Yoshida, Keizo Suzuki
    1978 Volume 51 Issue 1 Pages 11-15
    Published: 1978
    Released: April 19, 2006
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    The conformations and electronic structures of dibenzoyl peroxide (BPO) and the benzoyloxyl radical (PhCOO) were elucidated by means of closed-shell and restricted open-shell SCF MINDO/3 calculations. The dihedral angle of BPO between the two PhCOO planes was predicted to be 115°, and the barrier to the trans form of BPO was estimated to be very small. The ground state of the PhCOO radical was predicted to be of the ∑-type. The non-planar conformation of PhCOO was more stable (2 kcal/mol) than the planar one. The variation in the radical-pair property of the lowest state of acetyl peroxide during the homolytic dissociation process was estimated by the analysis of the two-configuration wavefunctions. The substituent effect on the rate of the homolytic dissociation of BPO was discussed in terms of the electronic structures of substituted BPO.
  • Akio Furusaki, Takeshi Matsumoto
    1978 Volume 51 Issue 1 Pages 16-20
    Published: 1978
    Released: April 19, 2006
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    The geometries, charge distributions, and heats of formation for 7-norbornyl, 7-norbornenyl, and 7-norbornadienyl cations have been calculated by the use of the semi-empirical MINDO/3 SCF MO method. Each of these cations is symmetrical with respect to the plane which contains the C(7)–H(7) bond and bisects the C(1)–C(7)–C(4) angle. Both the 7-norbornenyl and the 7-norbornadienyl cations take the nonclassical bridge-structure: the C(2)–C(3) and C(2)–C(7) distances are about 1.43 and 1.67 Å respectively, and the C(2)–C(1)–C(4)–C(7) dihedral angle is about 75°. The classical 7-norbornyl cation also is quite unsymmetrical with regard to the C(1)–C(7)–C(4) plane: the C(2)–C(1)–C(4)–C(7) and C(7)–C(1)–C(4)–C(5) dihedral angles are 94° and 144°, respectively. The calculated barriers to the bridge flipping in the 7-norbornyl and 7-norbornadienyl cations are 3.2 and 33.0 kcal/mol respectively. Although the latter is much higher than its observed value of 19.6 kcal/mol, it seems possible that solvation considerably lowers the barrier height. The present article also touches upon the solvolyses of derivatives of these carbocations.
  • Kiyoshi Kawakami, Tsutomu Mizoroki, Atsumu Ozaki
    1978 Volume 51 Issue 1 Pages 21-24
    Published: 1978
    Released: April 19, 2006
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    Dimerization of ethylene is highly selectively catalyzed by CoX(PPh3)3 (X=Cl, Br, and I) in the presence of Lewis acid in halobenzene under mild conditions. The catalytic activity is significantly affected by the solvent, bromobenzene being the most effective. The role of BF3·OEt2 seems to be formation of a one-to-one complex of Co(I) and BF3, since the rate of ethylene dimerization attains a plateau on addition of equimolar amount of BF3·OEt2. The isomerization of 1-pentene is enhanced by addition of molecular hydrogen or ethylene to the catalyst system. The isotopic scrambling between C2H4 and C2D4 takes place faster than dimerization. The results are in line with hydridocobalt intermediate formed by the oxidative addition of ethylene to Co(I) complex.
  • Susumu Yoshida, Ryozo Oyamada, Kazutaka Kawamura
    1978 Volume 51 Issue 1 Pages 25-27
    Published: 1978
    Released: April 19, 2006
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    Raman spectra of solid and molten ThCl4–KCl system were observed and the structure change of ThCl4 on melting from the octa-coordinate body-centered tetragonal type, D4h, to the tetra-coordinate tetrahedron type, Td, was studied. The decrease in frequency of the symmetric stretching vibration ν1 with decrasing ThCl4 concentration for molten ThCl4–KCl is interpreted as due to the presence of ThCl4, ThCl5, and ThCl73− complexes in the molten ThCl4–KCl mixture. Such a compositional dependence for ν1 appears to support the idea that, for a decrease in the ThCl4 concentration in molten ThCl4–KCl mixtures, the bond strength between the thorium and chloride ions decreases and the number of chloride ions around the thorium ion increases from 4 to 7.
  • Isao Kanesaka, Hideyuki Arai, Kiyoyasu Kawai
    1978 Volume 51 Issue 1 Pages 28-32
    Published: 1978
    Released: April 19, 2006
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    The finite element method was examined in relation to the two-dimensional vibrational Schrödinger equation. Some boundary conditions were used because of the symmetry of the potential, resulting in a higher precision in the case of the symmetrical potential, where the harmonic oscillators and the symmetrical hydrogen bond without anharmonicity were examined satisfactorily. An application was made to the symmetrical hydrogen bond with an-harmonicity, where the precision was less for the higher levels. By a comparison of the calculated with the observed infrared spectra, the anharmonic potential constants for the assumed potential function were estimated.
  • Yasumasa Ikezoe, Shoichi Sato
    1978 Volume 51 Issue 1 Pages 33-36
    Published: 1978
    Released: April 19, 2006
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    In the γ-radiolysis of carbon dioxide, the back reaction or reoxidation of carbon monoxide, proceeds at a moderate rate with propane concentration less than 0.5%, reducing the apparent G(CO) value. Concerning the total pressure and dose rate dependence of the G(CO) value with such small propane addition, it was found that the back reaction was accelerated by raising the total pressure and by lowering the dose rate. The following reactions of clustered negative ions are considered to explain the pressure and dose rate effects:
    X+CO→CO2+Y+Z1,
    X+C3H8→Y+Z2,
    X+X+mCO2+Z3,
    where X stands for a clustered negative ion.
  • Keiichi Fukuyama, Kensaku Hamada, Tomitake Tsukihara, Yukiteru Katsube
    1978 Volume 51 Issue 1 Pages 37-44
    Published: 1978
    Released: April 19, 2006
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    The absolute configuration of epishamixanthone has been determined from the Bijvoet differences by anomalous scattering of light atoms for Cu Kα radiation. To verify the determination, the absolute configuration of sterigmatocystin which was already determined has been examined by the same procedure. The reliability of the Bijvoet differences calculated from the structure has been estimated by means of the probability method. The errors in the measured values of the Bijvoet differences have been analysed by the normal probability plot. The accuracy of the measurement may be affected considerably by the habit of crystal. The present analysis has established that the configurations of two asymmetric carbon atoms in epishamixanthone are both R.
  • Yoshihiko Sadaoka, Yoshiro Sakai
    1978 Volume 51 Issue 1 Pages 45-48
    Published: 1978
    Released: April 19, 2006
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    Switching phenomena were observed in Au(+)–naphthacene (crystalline-state)–Al(−). The threshold voltage was found to be expressable as Vth∝ (thickness)2; in amorphous films no reproducible switching phenomena were observed within the same region of the field strength. The differences between them were discussed in terms of the trap density, which is closely related to the crystallinity of the evaporated films.
  • Minoru Kumakura, Kazuo Arakawa, Toshio Sugiura
    1978 Volume 51 Issue 1 Pages 49-53
    Published: 1978
    Released: April 19, 2006
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    The formation reactions of protonated molecular ions in acetaldehyde–trioxane mixtures have been studied with a modified time-of-flight mass spectrometer. From the analysis of the fine structure of the ionization efficiency curves of fragment and product ions obtained by means of the retarding potential differential technique using acetaldehyde-d4, the precursors of the product ions were determined. Protonated acetaldehyde is formed by the hydrogen atom transfer reaction of acetaldehyde molecular ion with trioxane, and protonated trioxane by the proton transfer reaction of CHO+ generated from acetaldehyde with trioxane. The rate constants of the formation reactions of the product ions in acetaldehyde (or ace taldehyde-d4)–trioxane mixtures were determined and isotope effect was observed. The CHO+ generated from acetaldehyde participated predominantly in the proton transfer reaction as compared with that generated from trioxane. From the proton transfer reaction involving thermal ion CHO+ generated from acetaldehyde it was found that the proton affinity of trioxane is smaller than that of acetaldehyde.
  • Minoru Kumakura, Kazuo Arakawa, Toshio Sugiura
    1978 Volume 51 Issue 1 Pages 54-57
    Published: 1978
    Released: April 19, 2006
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    The ion-molecule reactions in the binary mixture of ethylene oxide and trioxane have been studied with use of a modified time-of-flight mass spectrometer. As cross-reaction product ions, C3H5O2+, C3H6O2+, and C3H7O2+ were observed under the conditions of long delay times and elevated pressure. It was found that these ions are formed by the dissociation of unstable intermediate-complex resulting from the reaction of ethylene oxide molecular ion with trioxane. It was proposed that the complex is of cyclic structure in which positive charge is delocalized. From the consideration of isotopic distribution of the prodoct ions in ethylene-d4 oxide–trioxane mixtures, the skeletal structures of the product ions were investigated. The rate constants of the formation reactions of C3H5O2+, C3H6O2+, and C3H7O2+ in ethylene oxide–trioxane mixtures were found to be 2.20×10−10, 2.61×10−10, and 1.74×10−10 cm3 molecule−1 s−1 respectively.
  • Akio Yamamoto, Hiromu Murata
    1978 Volume 51 Issue 1 Pages 58-64
    Published: 1978
    Released: April 19, 2006
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    With special attention to calcium oxide, values obtained by NvT-ensemble Monte Carlo calculations are reported for the internal energy, pressure, heat capacity, thermal pressure coefficient, Grüneisen’s γ, and component radial distribution functions of ionized matter in the condensed phases. The calculations cover 14 vT points: seven points lying on one isochore at the X-ray density and eight on one isotherm at the normal melting point. Both thermodynamic quantities and structural properties in the vicinity of the melting point are indicative of the fluidsolid phase change. A brief comparison of the Monte Carlo results with the experimental data is also made.
  • Masao Onda, Yoshitomo Oshima, Ichiro Yamaguchi
    1978 Volume 51 Issue 1 Pages 65-69
    Published: 1978
    Released: April 19, 2006
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    The microwave spectrum of o-chlorophenol has been observed in the frequency range 10–34 GHz. The rotational and centrifugal distortion constants were obtained for two isotopic species, 35ClC6H4OH and 37ClC6H4OH. The analysis of the hyperfine structure gives the following nuclear quadrupole coupling constants for 35Cl species: χaa=−67.6, χbb=33.3, and χcc=34.3 (MHz). The spectrum assigned has been attributed to the cis-form (intramolecularly hydrogen bonded between Cl and HO) from a brief consideration of the relative intensity of the a-and b- type transitions. No significant effect of the intramolecular hydrogen bonding on the nuclear quadrupole coupling was observed.
  • Midori Goto, Eiichi Asada
    1978 Volume 51 Issue 1 Pages 70-74
    Published: 1978
    Released: April 19, 2006
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    The crystal structure of the A-super form of lauric acid has been determined. The structural parameters were refined by the block-diagonal least-squares method, and the final R value was 0.094. Two types of molecular conformations of a lauric acid exist in the crystal; one is the ordinary type, as seen in the C-form or the A1-form of the lauric acid, while the other is that rotating the carboxyl group about the C1–C2 bond. This unusual structure was explained by the oxygen-oxygen distance of the adjacent molecule.
  • Mitsuyasu Kawakami, Shuichi Kagawa
    1978 Volume 51 Issue 1 Pages 75-78
    Published: 1978
    Released: April 19, 2006
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    The solubility coefficients of hydrocarbons in unvulcanized natural rubber at 25 °C were determined by gas-liquid chromatography. Natural rubber was used as a stationary liquid and nine kinds of lower olefins and paraffins as solutes. The retention volume for all the solutes did not vary with sample size. It was found that the correction for gas phase imperfection is negligible. Thus the solubility coefficient was readily obtained from the specific retention volume without any correction. The values obtained were in fairly good agreement with those determined by the volumetric method given in other works. Modified equations expressing the relationships between the solubility coefficient and the boiling temperature, the critical temperature, and the Lenard-Jones force constant, which might be applicable to a more extensive range of gaseous compounds, were presented.
  • Akira Itaya, Ken-ichi Okamoto, Shigekazu Kusabayashi
    1978 Volume 51 Issue 1 Pages 79-84
    Published: 1978
    Released: April 19, 2006
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    The emission spectra of poly(N-vinyl-5H-benzo[b]carbazole) (PV5BCz) and poly(N-vinyl-7H-benzo[c]carbazole) (PV7BCz), which are prepared by radical and cationic polymerization, and their monomeric model compounds were investigated in solutions. In the case of PV7BCz, the fluorescence spectra were composed of a second excimer fluorescence at the shorter wavelength and a sandwich-like excimer fluorescence at the longer wavelength. The difference in the spectra between the radical and cationic polymers was quite similar to that of the poly(N-vinylcarbazole) (PVCz) system. The intensity of the sandwich-like excimer fluorescence was independent of the polymerization methods, but the intensity of the second excimer fluorescence increased with an increase in the content of the syndiotactic sequence. In the case of PV5BCz, the behavior of the fluorescence spectra of the radical polymers was similar to that of the PVCz and PV7BCz systems. On the other hand, the fluorescence spectra of the cationic polymers differed markedly from those of the above-mentioned polymers. The cationic polymers did not show the second excimer fluorescence, but a monomer-like structured fluorescence, at the shorter wavelength, although it did show the sandwich-like excimer fluorescence at the longer wavelength. This significant difference in the fluorescence spectra between the radical and cationic polymers is attributable to the difference between their tacticities. On the basis of these results, the characteristics of the second excimer site were further clarified.
  • Yasuo Tokoro, Makoto Misono, Toshio Uchijima, Yukio Yoneda
    1978 Volume 51 Issue 1 Pages 85-89
    Published: 1978
    Released: April 19, 2006
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    This paper deals with the analysis of the desorption curves for heterogeneous surfaces, where the activation energy of desorption, Ed, linearly depends on surface coverage, θ, i.e., Ed=Ed0+α(1−θ) Computer simulation resulted in a characteristic change of curve shapes corresponding to the variation of desorption rate parameters, Ed0, A and α. By means of empirical parameters characterizing the peak shapes such as peak temperature, half width and symmetry factor, we were able to obtain a set convenient and valid equations for estimating the rate parameters. The curve fitting method was also investigated and found to be more precise, the equations obtained being very useful for giving an initial set of values for this method. The two methods were applied to the thermal desorption curves of CO2 on TiO2, and found to be useful and reliable.
  • Nobuaki Inoue, Yoshio Matsunaga
    1978 Volume 51 Issue 1 Pages 90-93
    Published: 1978
    Released: April 19, 2006
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    Crystalline pyrene complexes with 2,4-dinitrofluorobenzene, 2,4-dinitrochlorobenzene, 2,4-dinitrotoluene, 2,4-dinitrophenol, and picryl chloride exhibit polymorphic transitions. Their temperatures and associated enthalpies are presented. The high-temperature forms show essentially identical X-ray diffraction patterns, losing the special natures of the substituents on the acceptor molecules. Isomorphism is supported by the formation of complete solid solutions demonstrated for combinations of these forms. The enthalpy and entropy of melting of the present complexes are characterized by rather small values, 4–6 kcal mol−1 and 12–14 cal deg−1 mol−1respectively, indicative of anomalously high thermal motion or disorder in the high-temperature forms. Marked changes in the spectral and electrical properties by the transitions are noted in some cases.
  • Susumu Kohda-Sudoh, Shigeyoshi Katagiri
    1978 Volume 51 Issue 1 Pages 94-97
    Published: 1978
    Released: April 19, 2006
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    The vertical transition energies of both the Rydberg and valence-shell type transitions of CH4 were calculated by the use of the ab initio SC-LCAO-MO method. We used Slater-type AO’s as the basis AO’s and added the extra-valence AO’s (3s, 3p, 4s, and 4p) of a carbon atom to the minimal-basis set in order to express the Rydberg MO’s. From the limited CI calculations, the mixing expressed in terms of the orthogonalized AO’s between the Rydberg and valence-shell transitions was shown to be little. The lowest two absorption bands near 9.7 and 11.7 eV were identified as a 3s-like Rydberg transition with a 3p-like one and a 4s-like Rydberg transition with a 4p-like one respectively. The total energy and Mulliken population analysis were also calculated and compared with the results of the minimal-basis calculations.
  • Hiroyuki Shinohara, Akira Imamura, Takahiro Masuda, Masaharu Kondo
    1978 Volume 51 Issue 1 Pages 98-102
    Published: 1978
    Released: April 19, 2006
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    The energy required to stretch a C–H bond of alkanes by 0.5 Å from an equilibrium bond length was calculated by the INDO method, and it was found that this energy has a relation with the delocalizability, DrR, of hydrogen atoms in alkanes, and with the activation energy for the hydrogen-abstraction reaction of the methyl radical from alkanes. The reactivities of hydrogen atoms in aliphatic alcohols and carboxylate ions, as defined by this energy were found to correlate with the partial reactivities of hydrogen atoms, just as was proposed by Anbar et al., i.e., the rate constants for the hydrogen-abstraction reaction of aliphatic compounds with hydroxyl radicals can be well explained by a summation of the partial reactivities assigned to primary, secondary, and tertiary hydrogen atoms bound to α- or β- (for γ-CH and δ-CH the same value as for β-CH was used) carbon atoms.
  • Kenji Akiyama, Yoshiyuki Morioka, Ichiro Nakagawa
    1978 Volume 51 Issue 1 Pages 103-107
    Published: 1978
    Released: April 19, 2006
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    The frequencies of the transverse (TO) and longitudinal (LO) modes of the infrared active vibrations of the crystal CsNiCl3 were obtained from the polarized far infrared reflection spectra. The polarized Raman spectra were also measured. The calculation of the TO and LO frequencies near the center of the Brillouin zone was made on the basis of a rigid ion model which includes effective ionic charges and interionic repulsive force constants. A set of potential constants and effective ionic charges were determined from the observed values of the TO and LO frequencies and Raman frequencies using the least-squares method. The short-range force constant associated with the nickel ion to the chlorine ion indicates that some amount of covalent character is included in this bond.
  • Yutaka Saito, Katsunosuke Machida
    1978 Volume 51 Issue 1 Pages 108-112
    Published: 1978
    Released: April 19, 2006
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    Infrared and Raman spectra of hydantoin and its C- and N,N′-deuterated derivatives in the solid state have been recorded. The fundamental frequencies were assigned by referring to isotopic frequency shifts and vibrational spectra of related compounds. Normal coordinate analysis was carried out by using a planar Cs molecular model. A simple Urey-Bradley force field was used for the stretching and the bending coordinates and a valence force field for the out-of-plane deformation and the torsional coordinates. The force constants were refined by the least squares method to reproduce the observed frequencies.
  • Tadatsugu Yoshikuni, Ryokichi Tsuchiya, Akira Uehara, Eishin Kyuno
    1978 Volume 51 Issue 1 Pages 113-115
    Published: 1978
    Released: April 19, 2006
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    Thermal trans-to-cis isomerization of [CrCl2(en)2](H5O2)Cl2 and [CrCl2(pn)2]Cl·1.5H2O was studied in the solid phase by derivatographic and isothermal measurements. The former complex was found to isomerize in anhydrous state after the complete elimination of hydrogen chloride and water, the latter in the temperature range for dehydration. The activation energies for the isomerization of these two complexes were isothermally estimated to be 202 and 193 kJ mol−1, respectively. The same type of isomerization mechanism is suggested for these complexes, differing from that for the corresponding cobalt(III) complexes in which lattice waters participate.
  • Koichi Saitoh, Nobuo Suzuki
    1978 Volume 51 Issue 1 Pages 116-120
    Published: 1978
    Released: April 19, 2006
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    A new theoretical treatment of the solute distribution in gel chromatography is proposed. Practical gel chromatography can be regarded as one based on a combined function of the molecular sieve effect and the partition effect. Introducing the concept of a regular solution to the column system of gel chromatography, the contribution of the partition effect can be estimated from the data on the physical properties of the solute, the solvent, and the gel matrix. The argument being proposed is supported by the experimental data on the gel chromatography of metal (II, III) chelates with acetylacetone and normal alkanes previously obtained in the systems of a poly(vinyl acetate) gel and various eluting solvents.
  • Ryoko Matsuzaki, Hagio Masumizu, Nagisa Murakami, Yuzo Saeki
    1978 Volume 51 Issue 1 Pages 121-122
    Published: 1978
    Released: April 19, 2006
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    The thermal decomposition of calcium sulfite at temperatures below 880 °C in an argon stream was examined. Also, the reaction between calcium sulfate and calcium sulfide, which were formed during the decomposition process of calcium sulfite, was examined. The thermal decomposition process of calcium sulfite can be represented as follows: on heating calcium sulfite, the reaction, CaSO3→CaO+SO2, occurs above about 600 °C. Above about 680 °C, the reaction, 4CaSO3→3CaSO4+CaS, occurs besides the above reaction. Furthermore, the reaction between calcium sulfate and calcium sulfide which are formed during the decomposition process of calcium sulfite, 3CaSO4+CaS→4CaO+4SO2, occurs above about 780 °C.
  • Yukito Murakami, Sunao Yamada, Yoshihisa Matsuda, Kazunori Sakata
    1978 Volume 51 Issue 1 Pages 123-129
    Published: 1978
    Released: April 19, 2006
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    Cobalt(III) corroles exist predominantly as polymeric species in a concentration range above 5×10−3 M in chloroform at room temperature as confirmed by NMR measurements. The coordination behavior of pyridine bases at the axial sites of cobalt(III) corroles, in a concentration range where they are present exclusively in the monomeric species, has been investigated by measuring electronic spectra in acetone at 25.0±0.1 °C. Penta- and hexa-coordination processes were found to take place, and the stepwise formation constants were interpreted by means of the equations logKi=a·pKa+b and logKiKi0=ρσ. When the cobalt corrole was reduced at the nuclear cobalt from trivalent to bivalent state, only one pyridine molecule was coordinated at its axial sites, hexa-coordination being no longer possible as confirmed by ESR measurements. The axial ligation behavior of cobalt corroles is quite analogous in nature to that of cobalt corrinoid.
  • Kunio Ohzeki, Katsunori Nozawa, Tomihito Kambara
    1978 Volume 51 Issue 1 Pages 130-133
    Published: 1978
    Released: April 19, 2006
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    The composition of hydrated copper(II), copper-pyridine, and -ammine species fixed on the cation exchange resin was determined by chemical and thermogravimetric analyses. Provided that all the water and bases were coordinated to copper(II) ion, the species on the resin were estimated to be [Cu(H2O)5]2+, [Cu(py)(H2O)3]2+, and [Cu(NH3)3(H2O)3]2+, respectively. The removal of copper(II) ion from the resin with 2-thenoyltrifluoroacetone (Htta) was studied in various organic solvents. The rate of reaction was accelerated with the replacement of water molecules coordinated to the metal ion with pyridine or ammonia.
  • Masao Kiyama
    1978 Volume 51 Issue 1 Pages 134-138
    Published: 1978
    Released: April 19, 2006
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    Manganese and cobalt ferrites were prepared by the air oxidation of aqueous suspension of Fe(OH)2 and either Mn(OH)2 or Co(OH)2 at 50–80 °C. In alkaline suspensions, all the metal ions are transformed into spinel ferrites, MxFe3−xO4 (M=Mn or Co), by a suitable combination of the oxidation temperature and the concentration of the excess NaOH. Both manganese and cobalt ferrites consist of ferromagnetic particles (ferrite(A)) when x is smaller than 1.3, nonferromagnetic particles (ferrite(B)) when x is larger than 2, and mixtures of the two in the intervening range. The contents of Mn or Co, both in a solid solution of hydroxides, Mx⁄3Fe1−x⁄3(OH)2, and in ferrite, increase with the progress of the formation of the ferrite(A) caused by oxidation. The formation of the ferrite(B) begins when x in the solid solution reaches 2. Each particle in the ferrite(A) is less homogeneous in comparison with that in the ferrite prepared by a solid-state reaction, although with the same composition. The difference in the homogeneity causes the essential difference in magnetic properties.
  • Yoneichiro Muto, Tadashi Tokii
    1978 Volume 51 Issue 1 Pages 139-142
    Published: 1978
    Released: April 19, 2006
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    Four complexes with the general formula of Cu[sal·(CH2)n·N(R)R′]Cl (sal=·\overset2O·C6H4·\overset1CH=N·; n=2 and 3; R=H and CH3; R′=CH3) were characterized by elemental analyses, IR and visible reflectance spectra, ESR spectra, and magnetic susceptibilities. The complexes where n=2, Cu[sal·(CH2)2·NHCH3]Cl and Cu[sal·(CH2)2·N(CH3)2]Cl, showed normal paramagnetic behavior. The Cu[sal·(CH2)3·N(CH3)2]Cl complex was obtained in two forms, one red-violet and the other green. The red-violet form showed the usual magnetic behavior expected for a mononuclear copper(II) complex, whereas the green one exhibited the antiferromagnetic behavior typical of binuclear copper(II) complexes. The magnetic properties of these complexes are discussed in terms of structural considerations. The characterization of the Cu[sal·(CH2)3·N(CH3)2Br complex is also reported.
  • Yuzo Nishida, Sigeo Kida
    1978 Volume 51 Issue 1 Pages 143-149
    Published: 1978
    Released: April 19, 2006
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    In order to investigate the ground state configuration of some square planar cobalt(II) complexes such as Schiff base complexes of the cis-[CoN2O2] type, whose ESR spectra are quite different from those of cobalt(II) phthalocyanine and porphyrins, the spin-orbit matrix based on the four zero-order wave functions, (yz)1, (xz)1,(z2)1, and (xy) were diagonalized on assuming reasonable values for necessary parameters. The result has clearly shown that an unpaired electron is localized in dyz orbital in the ground state for these complexes. ESR spectra of a series of cobalt(II) complexes with N4-macrocyclic ligands were measured and interpreted in terms of the conclusion obtained here.
  • Masayuki Dokiya, Kenzo Fukuda, Harumi Yokokawa, Tetsuya Kameyama
    1978 Volume 51 Issue 1 Pages 150-153
    Published: 1978
    Released: April 19, 2006
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    A two-step decomposition process of hydrogen sulfide was studied. The process is constituted from a hydrogen-evolution step (CO+H2S\oversetca.200°C→H2+COS) and a carbonyl sulfide-decomposition step (COS\oversetca.830°C→CO+1⁄x·Sx. Almost an equilibrium amount of hydrogen could be produced in the first reaction (ca. 40%, 200 °C, 1 atm, CO/H2S=2.2) with a cobalt sulfide or nickel sulfide catalyst. In the second reaction, an almost equilibrium amount of carbonyl sulfide (45%) could also be decomposed into carbon monoxide and elementary sulfur at 830 °C under 1 atm with a sufficient reaction rate and selectivity without using any catalysts. Carbon dioxide was formed as a by-product in the second reaction: however, its yield was only 5% of the carbon monoxide produced. From these results, it may be concluded that this two-step decomposition process of hydrogen sulfide can produce more hydrogen than that produced by the direct decomposition of hydrogen sulfide. In the second reaction, however, the recombination of carbon monoxide with elementary sulfur can not be neglected. Thus, a rapid separation of sulfur from carbon monoxide is required.
  • Shunichi Nishikida, Shigero Ikeda
    1978 Volume 51 Issue 1 Pages 154-158
    Published: 1978
    Released: April 19, 2006
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    The energy shifts of X-ray excited Auger electrons and photoelectrons for zinc and magnesium in their metals, oxides, halides, and chelate compounds are analyzed in terms of the relaxation effect. Zn 2p3⁄2, 3d photoelectron, Zn L3M45M451G Auger electron, Mg 1s, 2p photoelectron and Mg KL23L231D Auger electron peaks were provided for the investigation. The quantitative estimation of the extra-atomic relaxation energies for core electron emission was performed by combining atomic spectral data, XPS and AES data of the compounds. For zinc compounds, extra-atomic relaxation energies increase in the order of ZnF2<ZnCl2<ZnBr2≈ZnO<ZnI2≈ZnS<Zn(acac)2, whilst the values are not fairly systematic for magnesium compounds. The nearest neighbored atom is found to be the important function for the extra-atomic relaxation energies.
  • Reiko Saito, Yoshinori Kidani
    1978 Volume 51 Issue 1 Pages 159-163
    Published: 1978
    Released: April 19, 2006
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    Two types of copper(II) complexes, Cu(c-chxn)2X2·nH2O and Cu(t-chxn)2X2·nH2O (X=Cl, Br, NO3, and ClO4, n=0–2), and three types of nickel(II) complexes, [Ni(c-chxn)2]X2, [Ni(c-chxn)3]X2·nH2O (X=Cl, Br, NO3, and ClO4, n=0.5–1.5) and [Ni(t-chxn)2(H2O)2]X2 (X=Br and ClO4), were synthesized. Here, c-chxn and t-chxn stand for cis- and trans-1,2-cyclohexanediamine respectively. Based upon the analyses of the electronic spectra and magnetic moments, the structures of the copper(II) complexes synthesized were found to be distorted octahedrons. The influence of the steric configurations of the diamine isomers on the structures of the copper(II) complexes is small. The three types of nickel(II) complexes were found to have square planar, octahedral, and distorted octahedral structures respectively. The steric influence of the ligands on the properties of the nickel(II) complexes was also considered.
  • Tomozo Koh, Kazuo Taniguchi, Iwaji Iwasaki
    1978 Volume 51 Issue 1 Pages 164-168
    Published: 1978
    Released: April 19, 2006
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    An accurate method has been proposed for the determination of pentathionate in mixtures with thiosulfate and sulfite. The method is based on the formation of thiosulfate equivalent to the pentathionate, and the spectrophotometric determination of excess iodine for the reaction with the thiosulfate formed. The conditions for pentathionate to be quantitatively converted into thiosulfate were established by varying pH, reaction time, and amounts of sulfite. The method can be successfully applied to the determination of pentathionate, thiosulfate, and sulfite when they are mixed in various ratios, giving a relative standard deviation of 0.82% at the 0.5 μmol level of pentathionate in a 10.0 cm3 sample solution in the presence of 0.5 μmol of thiosulfate and 0.25 μmol of sulfite.
  • Taro Saito
    1978 Volume 51 Issue 1 Pages 169-173
    Published: 1978
    Released: April 19, 2006
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    Bis(dimethylglyoximato)halogenocobalt(III) complexes of benzoyl(1-pyridinio)methanide were synthesized by a new kind of oxidative addition reaction of N-phenacylpyridinium halides to diaquabis(dimethylglyoximato)cobalt(II) in air. The crystal structure of the [benzoyl(1-pyridinio)methanide]chlorobis (dimethylglyoximato) cobalt(III) toluene solvate was solved by single-crystal X-ray diffraction techniques. The crystals are monoclinic (space group P21/c), with cell dimensions of a=11.41(1), b=10.28(1), c=27.50(3) Å, β=116.3(1)°, and Z=4. The final R was 0.068. The ylide ligand coordinates to cobalt through the ylide carbon, with a Co–C distance of 2.07(1) Å, and the chlorine atom is bonded to cobalt with a Co–Cl distance of 2.285(4) Å and with a C(ylide)–Co–Cl bond angle of 175.5(3)°. The dimethylglyoxime ligands and cobalt atom are co-planar to within 0.04 Å.
  • Masashi Inoue, Toshio Sugita, Katsuhiko Ichikawa
    1978 Volume 51 Issue 1 Pages 174-178
    Published: 1978
    Released: April 19, 2006
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    The reaction of anisole with propylene oxide by aluminum chloride has been studied in various kinds of solvents. While the normal Friedel-Crafts reaction yielded 2-(methoxyphenyl)-1-propanols, 1,1-bis(methoxyphenyl)-propanes were also formed in this reaction; these were not obtained by the subsequent reaction of mono(methoxyphenyl) products with another anisole. The yields of 1,1-bis(methoxyphenyl)propanes increased by increasing the basicity of solvents. The mechanism of the formation of 1,1-bis(methoxyphenyl)propanes can be explained by the isomerization of epoxide to aldehyde and the subsequent condensation with anisole. Various kinds of epoxides also gave 1,1-bis(methoxyphenyl)alkanes in nitromethane.
  • Hiromichi Besso, Kimiaki Imafuku, Hisashi Matsumura
    1978 Volume 51 Issue 1 Pages 179-181
    Published: 1978
    Released: April 19, 2006
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    The reaction of 4H-pyran-4-thiones with ammonia gave 4(1H)-pyridinethiones or bis(4-pyridyl) disulfide, while that of 3-methoxy-2-methyl-4H-pyran-4-thione with guanidine gave the 1,3-thiazine derivative. 4H-Pyran-4-thiones reacted with hydrazine to afford pyridazines, pyrazoles, and 1-amino-4(1H)-pyridinethiones. 4H-Pyran-4-thiones having the hydroxyl group in the β-position gave the pyridazine derivatives.
  • Kenichiro Arai, Yoshitaka Ogiwara
    1978 Volume 51 Issue 1 Pages 182-184
    Published: 1978
    Released: April 19, 2006
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    The formation of a reversed micelle by dodecylbenzenesulfonic acid in benzene containing a certain amount of water was examined by means of the absorption spectra of the Methylene Blue added to the system. The hydrolysis of the sucrose secondary-solubilized in the system was then investigated. The maximum rate enhancement of 400-fold was obtained in the presence of the micelle on the basis of the reaction in an aqueous solution in the presence of hydrochloric acid, whereas the addition of ethanesulfonic acid to the system showed only a little effect on the reaction rate. The reaction rates were found to show behavior similar to that of the stability of the micelle with respect to changes in the substrate concentration and in the amount of solubilized water. From these results, the greater part of the rate enhancement obtained in the present system might be concluded to result from some effects due to the formation of the reversed micelle.
  • Masakatsu Matsumoto, Satoshi Dobashi, Kiyosi Kondo
    1978 Volume 51 Issue 1 Pages 185-187
    Published: 1978
    Released: April 19, 2006
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    The sensitized photooxygenation of several 9-vinylphenanthrenes in carbon tetrachloride was investigated. In the cases of 9-vinyl- and 9-(β-substituted vinyl) phenanthrenes, the 1,4-cycloaddition of singlet oxygen to a conjugated system composed of the side chain and 9,10-double bond of the ring surpassed other oxidation modes, i.e., the “ene” reaction and 1,2-cycloaddition of singlet oxygen, to give the 1,2-dioxatriphenylene-type peroxides. On the other hand, the sensitized photooxygenation of 9-isopropenylphenanthrene gave a hydroperoxide due to the “ene” reaction.
  • Yasukazu Ohkatsu, Teiji Tsuruta
    1978 Volume 51 Issue 1 Pages 188-191
    Published: 1978
    Released: April 19, 2006
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    Autoxidation reactions of saturated and unsaturated hydrocarbons were carried out using Co(II) tetra(p-tolyl)porphyrin as the catalyst in ethyl acetate at 30°C The Co(II) complex activated the oxygen molecule to the superoxide ion, which abstracted a hydrogen atom from a saturated hydrocarbon or added to the double bond of an unsaturated hydrocarbon, to initiate autoxidation. The reactivity of the activated oxygen molecule was found at the site of the free radical rather than that of the anion thereof. The reactivities were compared with those of superoxide ions derived from other origins.
  • J. Yasuo Satoh, C. Akira Horiuchi, Akira Hagitani
    1978 Volume 51 Issue 1 Pages 192-195
    Published: 1978
    Released: April 19, 2006
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    3α-Alkyl-5β-cholestan-2-one (R=CH3, C2H5, and CH3CH2CH2) was prepared by the direct alkylation of 5β-cholestan-2-one with alkyl iodide and potassium t-butoxide in a reflux of t-butyl alcohol-benzene. The 3α-benzyl ketone was prepared from 5β-cholestan-2-one by aldol condensation with benzaldehyde in the presence of potassium hydroxide, followed by hydrogenation of the condensation product. The bromination of these 3α-alkyl ketones gave 3β-bromo-3α-alkyl-5β-cholestan-2-ones.
  • Takehiro Abe, Yusaku Ikegami
    1978 Volume 51 Issue 1 Pages 196-200
    Published: 1978
    Released: April 19, 2006
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    Appearance of p-dinitrobenzene anion radical has been demonstrated by visible and ESR spectroscopy in the replacement of the one nitro group of p-dinitrobenzene by hydroxide ion in aqueous dimethyl sulfoxide. The formation of the anion radical seems to be due to the direct electron transfer from hydroxide ion to p-dinitrobenzene. The results of kinetic studies suggest that the anion radical is a precursor in the substitution reaction.
  • Hajime Matsushita, Yasuko Tsujino, Masao Noguchi, Masahiko Saburi, Sad ...
    1978 Volume 51 Issue 1 Pages 201-204
    Published: 1978
    Released: April 19, 2006
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    Optical activation of 2-phenylpropionaldehyde (PPA) via enamines using L-proline derivatives as amine components was studied. S(+)-PPA was obtained when R(−)-2-methylpyrrolidine and S(−)-2-ethoxycarbonylpyrrolidine were used, while R(−)-PPA was obtained when S(−)-prolinamide, N-(L-prolyl)pyrrolidine, N-(L-prolyl)piperidine, S(+)-2-(1-pyrrolidinylmethyl)pyrrolidine, and S(+)-2-(piperidinomethyl)pyrrolidine were used. This suggests that there are two mechanisms for optical activation.
  • Saburo Aimoto, Yasutsugu Shimonishi
    1978 Volume 51 Issue 1 Pages 205-213
    Published: 1978
    Released: April 19, 2006
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    The following derivatives of hen egg-white lysozyme were prepared from native hen egg-white lysozyme, 2-chlorobenzyloxycarbonyl-lysozyme, S-(4-methylbenzyl)-reduced-lysozyme, and 2-chlorobenzyloxycarbonyl-S-(4-methylbenzyl)-reduced-lysozyme. Treatment of these derivatives with anhydrous liquid hydrogen fluoride for 90 min at 0 °C yielded fully active lysozyme with recoveries, in order, of 23, 12, and 7.4%. The properties of the lysozyme recovered were identical with those of native hen egg-white lysozyme, and crystals of this material were indistinguishable from those of native enzyme.
  • Hiroshi Nakanishi, Hitoshi Fujita, Osamu Yamamoto
    1978 Volume 51 Issue 1 Pages 214-218
    Published: 1978
    Released: April 19, 2006
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    The 13C NMR spectra of t-butyl formate (1), 1,1-diethylpropyl formate (2), and 2,6-dimethylphenyl formate (3) were measured at various temperatures. It was found that the signals of the trans and cis isomers in 1 and 2 are separated at very low temperatures, and that the signal of 3 only shows a slight line broadening. The complete line shape analyses of these temperature-dependent spectra were performed. The activation energies Ea(t-c) of the isomerization from the trans isomer to the cis were determined to be 10.9 kcal/mol for 1 and 7.2 kcal/mol for 2.
  • Takashi Ando, Junko Yamawaki, Yoshimasa Saito
    1978 Volume 51 Issue 1 Pages 219-224
    Published: 1978
    Released: April 19, 2006
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    The tide compounds, Ph(CH2)nOMns (n=2–6), were solvolyzed in buffered trifluoroacetic acid in order to elucidate the effect of a phenyl group at a remote position on the reactivity and the course of the reaction. The reactivities varied remarkably with the length of the alkyl chain(n); 2>>3<<4>5>6. The rate enhancement was attributed to anchimeric assistance by a remote phenyl group, and the rate depression to the electron-withdrawing inductive effect of a phenyl group. Studies on reaction products revealed that in trifluoroacetolysis of 4-phenylbutyl menasylate (n=4) the only pathway to take place is the one with δ-phenyl participation, and that even for 5-phenylpentyl menasylate (n=5) 12% of the reaction proceeds via ε-phenyl participation.
  • Takamasa Kinoshita, Toshio Miwa
    1978 Volume 51 Issue 1 Pages 225-228
    Published: 1978
    Released: April 19, 2006
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    The title compounds, methyl 5-deoxy-3-C-hydroxymethyl-2,3-O-isopropylidene-β-DL-lyxo-furanoside, and ribofuranoside derivatives were conveniently synthesized via the Birch reduction of 2-methyl-3-furoic acid, and the latter was identified with the sample prepared from D-xylose.
  • Takahiko Iwasaki, Shoji Kajigaeshi, Shuji Kanemasa
    1978 Volume 51 Issue 1 Pages 229-233
    Published: 1978
    Released: April 19, 2006
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    Peri- and stereoselective cycloadducts were obtained from the reactions of 8-aryl-8-azaheptafulvenes with some sulfenes. 8-Aryl-8-azaheptafulvenes reacted with phenylsulfene to give cis [8+2] cycloadducts as the sole products which would have resulted either from the endo approach or via the endo intermediate of the two reagents. On the other hand, with benzoylsulfene trans [8+2] cycloadducts were isolated. The formation of the latter products was rationalized by considering epimerization of the initially formed cis adducts. The cis [8+2] cycloadducts to vinylsulfene did not give the trans isomers but the hydrogen migrated derivatives under the influence of bases. The mechanism of the above reactions is also discussed.
  • Akio Murai, Hiroshi Sasamori, Tadashi Masamune
    1978 Volume 51 Issue 1 Pages 234-242
    Published: 1978
    Released: April 19, 2006
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    Several 11-substituted 17α-acetyl-12,13-epoxyetiojervanes were prepared from jervine. Jervine was degraded by a known process into (17E)-17-ethyletiojerva-4,12,17(20)-triene-3,l 1-dione, which on epoxidation followed by acid treatment gave 17α-ethyletiojerva-4,12-diene-3,l 1,20-trione as the main product. Acetalization of the carbonyl groups, at C3 and C20 of the triketone and subsequent hydride reduction produced two 11-epimeric alcohols, which on hydrolysis afforded 17α-ethyl-11α-hydroxyetiojerva-4,12-diene-3,20-dione and its 11β-hydroxy epimer. These alcohols and their acetates were oxidized with perbenzoic acid and/or t-butyl hydroperoxide to give the epoxides. The structure and configuration of these epoxides and the synthetic intermediates were determined on the basis of the chemical and spectral evidence.
  • Akio Murai, Hiroshi Sasamori, Tadashi Masamune
    1978 Volume 51 Issue 1 Pages 243-247
    Published: 1978
    Released: April 19, 2006
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    The title compound, one of the most important starting materials for the synthesis of C-nor-D-homosteroid and normal steroid hormones, was determined to possess (E)-configuration at the 17,20-double bond on the basis of chemical and spectral evidence.
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