Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 49 , Issue 12
Showing 1-50 articles out of 78 articles from the selected issue
  • Masamichi Akimoto, Masao Akiyama, Etsuro Echigoya
    1976 Volume 49 Issue 12 Pages 3367-3371
    Published: 1976
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The oxidation of propylene with Cu2O as active phase for acrylaldehyde formation gave no acrylaldehyde in contrast to the fully oxidized CuO–SiC. However, CuO–SiC from which adsorbed oxygen species was eliminated gave rise to the formation of a negligible amount of acrylaldehyde. The presence of molecular oxygen species adsorbed on the CuO–SiC was shown by the desorption of oxygen and the isotopic mixing reaction of 16O–18O. The adsorbed oxygen (possibly molecular oxygen species) seems to be necessary as oxygen incorporated into acrylaldehyde. Agreement of the ratio of 18O/16O in acrylaldehyde formed by the oxidation with oxygen containing 18O over Cu216O with that of 18O/16O in the reaction mixture supports the role of adsorbed oxygen species. The presence of O2 over Cu2O during the course of oxidation was confirmed by the formation of furan and maleic anhydride in the co-oxidation with butadiene. The results were discussed in relation to the structure of the catalyst suitable for selective oxidation, the incorporation of oxygen atom via electronegative oxygen species adsorbed being proposed.
  • Shiro Yoshizawa, Zenichiro Takehara, Zempachi Ogumi
    1976 Volume 49 Issue 12 Pages 3372-3375
    Published: 1976
    Released: April 19, 2006
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    The packed-bed electrode has been investigated in order to scale up the cell capacity by introducing three-dimensional electrode. The reactions of aniline formation by cathodic reduction of nitrobenzene and Fe(II) ion formation by cathodic reduction of Fe(III) ion were studied. When bed particles with high electric conductivity were used, the effective depth of the packed-bed where the electrode reaction took place was very small. However, when particles with moderate resistance were used, the effective depth increased. This is because the potential distribution in the bed material is the same as that in the electrolyte in the bed, the potential difference between particles and electrolyte thus being maintained constant at any position in the bed. From the standpoint of scaling up the cell capacity, this type of electrode can be effectively applied.
  • Kazuo Mukai, Takashi Kamata, Toshiko Tamaki, Kazuhiko Ishizu
    1976 Volume 49 Issue 12 Pages 3376-3381
    Published: 1976
    Released: April 19, 2006
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    The ENDOR spectra of ten kinds of phenylgalvinoxyl derivatives in solution have been observed, and the hyperfine splitting constants have been determined. The formally equivalent four meta ring protons of the galvinoxyl skeleton in the phenylgalvinoxyl radical become magnetically nonequivalent in two groups of two. This behavior may be explained by assuming that splittings arising through pure spin polarization, or through mixed hyperconjugation and spin polarization, are different for syn and anti meta ring protons of the phenylgalvinoxyl radical. A similar effect has been observed in the ENDOR spectra of other phenylgalvinoxyl derivatives. In radicals with a large substitution group at the meta or para position of the phenyl ring, the galvinoxyl skeleton twists unsymmetrically on either side; thus, all or three among the four meta ring protons become magnetically nonequivalent. The solvent dependence of the ENDOR spectra of the phenylgalvinoxyl radicals constituted strong evidence for the importance of the solvent in fixing the conformation and symmetric property of the radical molecules. The proposed analyses of the ENDOR spectra were also supported by the McLachlan Molecular Orbital calculations.
  • Masashi Tanaka
    1976 Volume 49 Issue 12 Pages 3382-3388
    Published: 1976
    Released: April 19, 2006
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    The polarized reflection spectra of the fluorene, carbazole, and dibenzofuran crystals have been measured from 30000 to 53000 cm−1 and the absolute intensity of the absorption parallel to the a, b, and c axes of these crystals has been obtained by the Kramers-Kronig transformation; these data allowed an interpretation to be made for the solution spectra. Furthermore, the influence of the intermolecular interaction on each level has been examined. This analysis shows that the lowest excited state of the fluorene molecule is the B2 state, while those of the carbazole and dibenzofuran are the A1 states. In fluorene, the sum of the oscillator strengths of the transition to two lower excited states (α and α* states) is 0.39 in the molecule and 0.61 in the crystal. Such hyperchromism is also observed in the α, p, and β states of carbazole and the β state of dibenzofuran. On the other hand, the α* state of dibenzofuran is hypochromic and the oscillator strengths in the molecule (0.87) decrease to 0.36 in the crystal. However, the factor group splitting and the crystal field shift are small and a one to one correspondence can easily be obtained between the solution and crystalline spectra.
  • Shigeto Kitahara
    1976 Volume 49 Issue 12 Pages 3389-3393
    Published: 1976
    Released: April 19, 2006
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    The Aerosil surface was treated with C1–C4 alcohols under both high-pressure and low-pressure conditions. The high-pressure treatment was carried out at various temperatures up to 250 °C using an autoclave, while the low-pressure treatment was done at 280 °C under vapor pressure at room temperature. The surface changes were followed by IR spectroscopy, and the carbon content was determined. The degrees of alkoxylation (OR groups/100 Å2) of the Aerosils treated sufficiently under low pressures were 1.3–1.6, approximately equal to the amount of OH isolated before the treatment, while the values under high pressures reached 2.3–3.4, equal or near to the amount of the total OH. The values for methoxylation were particularly higher, while those for t-butoxylation were quite low. These results, in addition to the observation of the IR spectra, indicate that the isolated OH groups are predominantly esterified under low pressures, while under high pressures the vicinal OH groups are esterified as well, and the opening of the siloxane bonds occurs easily in the case of methoxylation. The stability of the alkyl groups on the Aerosil against heating decreased in the order of: primary>secondary>tertiary.
  • Fujio Takahashi, Ryoichi Kikuchi
    1976 Volume 49 Issue 12 Pages 3394-3397
    Published: 1976
    Released: April 19, 2006
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    The NAD+ (nicotinamide adenine dinucleotide) reduction was carried out under illumination by using a platinum electrode coated with chlorophyll and quinone. Various quinones and β-carotene were used as components of the cathode layer to obtain a higher current density. The highest current density, 13 μA/cm2, was obtained in the case in which the cathode layer contained 0.01 μmol/cm2 of chlorophyll and the molar ratio of chlorophyll: chloranil : β-carotene was 1 : 1 : 2. The role of quinone and β-carotene in the cathode layer was discussed.
  • Tadashi Okada, Takeshi Mori, Noboru Mataga
    1976 Volume 49 Issue 12 Pages 3398-3402
    Published: 1976
    Released: April 19, 2006
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    The mechanism of the quenching of pyrene fluorescence by primary and secondary amines has been studied by means of fluorescence measurements and transient absorption measurements with the use of laser photolysis as well as conventional flash photolysis methods. It has been confirmed that 1-hydro-1-pyrenyl radicals and amino radicals are produced in the course of the fluorescence quenching reaction. The relative yields of 1-hydro-1-pyrenyl radicals for various amine quenchers were estimated.
  • Kazuo Tajima
    1976 Volume 49 Issue 12 Pages 3403-3407
    Published: 1976
    Released: April 19, 2006
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    The surface tension and adsorption were observed by the Wilhelmy plate and radiotracer methods at the air-solution interface of an aqueous solution of urea and α-dodecyl-ω-hydroxyhexa(oxyethylene) (D(EO)6). The adsorption of D(EO)6 was dependent on the concentration of urea below the CMC values, but above the values it was independent of the concentration. Urea adsorption occurs positively for low-surface packing of the poly(oxyethylene) group of D(EO)6, but negatively for the closest packing of the group and high concentrations of urea. It was confirmed that D(EO)6 adsorption took place at the solution surface according to the Gibbs adsorption isotherm, which was taken into account as an activity coefficient in an empirical equation for the interactions of D(EO)6 and urea in solution. Urea adsorption for the adsorbed monolayer of D(EO)6 above the CMC value was interpreted assuming that urea, as for the nonionic micelle, was non-penetrating, which was examined by gel permeation.
  • Keizi Hashimoto, Shozi Watanabe, Kimio Tarama
    1976 Volume 49 Issue 12 Pages 3408-3412
    Published: 1976
    Released: April 19, 2006
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    In order to reveal the formation mechanism of the active species in ethylene polymerization, the reduction of three kinds of molybdenum oxides, I, II, and III, which are insoluble in aq 10 M-NH3, soluble in aq NH3 but insoluble in water, and soluble in water respectively, was studied under a hydrogen pressure of 170 Torr over the temperature range 350–450 °C. The reduction rate of oxides I and II followed Elovich kinetics with a variable activation energy which increased with the progress of reduction, while that of III followed Elovich kinetics in the multiple kinetic stages and the minimum in apparent activation energy for the reduction lies at the reduction extent of MoO2.7−2.6. The final states of reduction of I, II, and III were MoO2.8−2.6, MoO2.0 and MoO2.2−2.1, respectively. The amount of Mo(V) in each oxide was determined by ESR measurements. The results indicate that Mo(V) in the II is related to the decrease of the apparent activation energy on reduction of III through their mutual interaction. A formation mechanism of the active species, Mo(V) in III, was proposed.
  • Kozo Fujii, Seiji Yoshino, Kinsi Motomura, Makoto Nakamura, Ryohei Mat ...
    1976 Volume 49 Issue 12 Pages 3413-3419
    Published: 1976
    Released: April 19, 2006
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    Equilibrium spreading pressure were measured at various compositions and temperatures for mixed systems of tridecanoic acid-myristic acid, myristic acid-pentadecanoic acid, and pentadecanoic acid-palmitic acid, and thermodynamical treatment of these data with respect to the equilibrium between crystal and monolayer was performed. By evaluating the equilibrium composition of monolayer phase from the measured curve of equilibrium spreading pressure vs. composition of solid phase, the phase diagram was constructed. It was found that the equilibrium curve has a maximum point where the solid and monolayer phases have the same composition and a point where the solid phase is in equilibrium with two monolayer phases. The partial molar enthalpy change accompanied by the phase transition from solid to monolayer were found to be dependent on the composition.
  • Jun Nakagawa, Kazunori Kuwada, Michiro Hayashi
    1976 Volume 49 Issue 12 Pages 3420-3432
    Published: 1976
    Released: April 19, 2006
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    The microwave spectra of gauche-ethanethiol and its isotopic species were studied. Most of the observed spectra for the species having the plane of symmetry exhibited doublet structures with large spacings due to the internal rotation of the mercapto group. The rs structure of the gauche isomer was determined from the observed moments of inertia. The gauche isomer whose dihedral angle τ(CCSH) is 61°45′±58′ has structural parameters close to those for the trans isomer except the angles around the carbon atom in the methylene group. The difference in angle values around the carbon atom in the methylene group between the trans and gauche isomers can be explained by the 3°7′ tilt of the methylene group towards the lone pair electrons on the sulfur atom. The direction of the dipole moment in the molecule was discussed on the basis of data given by Schmidt and Quade. The potential barrier of the mercapto internal rotation was obtained from splittings of the observed spectra. The Fourier coefficients of this barrier are V1=−207±67, V2=−386±27, and V3=1305±20 cal/mol. The spectra due to the excited methyl and mercapto torsional states were also measured for the trans and gauche isomers. The potential barrier of the methyl internal rotation for the trans isomer was found to be 3260±30 cal/mol from splittings of the spectra due to the first excited methyl torsional state.
  • Itsuo Iida, Junko Kato, Kenzi Tamaru
    1976 Volume 49 Issue 12 Pages 3433-3436
    Published: 1976
    Released: April 19, 2006
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    The catalytic isotope exchange reaction between deuterium gas and the water pre-adsorbed on Pt/Al2O3 was studied. At reaction temperatures above 273 K, the exchange rate was proportional to the deuterium pressure and independent of the amount of adsorbed water, which suggests that the rate determining step is the supply of deuterium from the gas phase. Its apparent activation energy was 38 kJ mol−1. Below freezing point of water, the kinetic behaviour was different from that above freezing point. At higher deuterium pressures the rate dropped abruptly at 273 K. Below the temperature the apparent activation energy was 54 kJ mol−1 and the exchange rate depended not on the deuterium pressure but on the amount of the pre-adsorbed water. At lower pressures, however, the kinetic behaviour was the same as that above 273 K, till the rate of the supply of deuterium from the gas phase exceeded the supply of hydrogen from adsorbed water to platinum surface.
    These results suggest that below 273 K the supply of hydrogen is markedly retarded, the state of the adsorbed water differing from that above 273 K. It was also demonstrated that when the adsorbed water is in the state of capillary condensation, the exchange rate becomes very small.
  • Yukio Aoki, Makoto Misono, Yukio Yoneda
    1976 Volume 49 Issue 12 Pages 3437-3440
    Published: 1976
    Released: April 19, 2006
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    Elimination reactions of 2-bromobutane and 2,3-dibromobutane over silica gels in which silanol protons on the surface were exchanged with bivalent ions such as Ba(II), Ca(II), Mg(II), and Ni(II) have been investigated. Dehydrobromination of 2-bromobutane was found to proceed mainly with syn elimination. Debromination by anti mode and non-stereospecific dehydrobromination were observed for 2,3-dibromobutane. The catalytic activities of these silica gels exhibit reversed volcano-type patterns when they are plotted against the electronegativity of metal ion together with those of alkali-ion exchanged silica gels. Reaction intermediates consistent with the stereochemistry observed are a s-butyl cation and a bromonium ion, respectively for 2-bromobutane and 2,3-dibromobutane.
  • Jun Nakagawa, Michiro Hayashi
    1976 Volume 49 Issue 12 Pages 3441-3448
    Published: 1976
    Released: April 19, 2006
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    In order to determine the molecular structure and barrier to internal rotation of the GeH3 group, the microwave spectra of (chloromethy)germane and its deuterated species ClCH2GeD3 have been investigated. From splittings of the spectra due to the first excited GeH3 torsional state, the barrier to internal rotation was determined to be 1740±30 cal/mol. Assuming the cylindrical symmetry of the C–Cl bond, the quadrupole coupling constant was determined to be χzz=−74.7 MHz for the 35ClCH274GeH3 species.
  • Mitsuyasu Kawakami, Makoto Egashira, Shuichi Kagawa
    1976 Volume 49 Issue 12 Pages 3449-3453
    Published: 1976
    Released: April 19, 2006
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    A gas-liquid chromatographic technique was employed to measure the thermodynamic properties of the solutions consisting of polyethylene glycol (PEG) and some organic compounds. Three kinds of PEG with different molecular weights were used as a stationary liquid, and six kinds of organic compounds as a solute. For most of the compounds examined, the retention volume varied with the sample size injected. By using the retention volume at an infinitesimal sample size, thermodynamic properties of organic compounds at infinite dilution in PEG, such as the activity coefficient based on weight fraction, Henry coefficient based on weight fraction, and the partial molar excess enthalpy, were determined. From the results it was found that the particular interactions between organic compounds and PEG such as the hydrogen bond formation is not significant, and the solutions can be regarded as a regular solution. The solubility parameters of PEG-600, -1000, and -4000 at 67.3 °C were found to be 10.0, 9.8, and 9.5, respectively.
  • Shoji Fujisawa, Isao Oonishi, Junji Aoki, Satoshi Iwashima
    1976 Volume 49 Issue 12 Pages 3454-3456
    Published: 1976
    Released: April 19, 2006
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    The crystals of naphthanthrone(C19H10O) are orthorhombic, with the P212121 space group and these lattice constants: a=17.345(17), b=3.973(13), c=17.392(14) Å, and Z=4. The structure was solved by the Patterson method and refined by a block-diagonal least-squares program to give an R-value of 0.085 on the basis of the 897 observed reflections collected by Weissenberg photographs. The molecule is planar within the limits of experimental error and has an approximate symmetry of mm. The molecules are stacked face-to-face by van der Waals forces along the b-axis. The interplanar spacing is 3.50 Å.
  • Gohsuke Sugihara, Mitsuru Tanaka
    1976 Volume 49 Issue 12 Pages 3457-3460
    Published: 1976
    Released: April 19, 2006
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    The pH and pNa of aqueous solutions of sodium deoxycholate (SDC) were measured at various temperatures. The critical micelle concentrations (CMC) were determined by means of the crooked points on the plot of pH or pNa vs. the SDC concentration. The data obtained were interpreted thermodynamically, and changes in the enthalpy and entropy of micellization were evaluated, from which it was concluded that the hydrogen bond plays a very important role in the micelle formation.
  • Tomoyasu Nakamura, Yasumasa J. I’Haya
    1976 Volume 49 Issue 12 Pages 3461-3465
    Published: 1976
    Released: April 19, 2006
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    Optical rotational strength for the n-π* transition of (R)-3-methylcyclohexanone is calculated by the CNDO/2 and INDO methods and compared with the observed values at 81 and 300 K, taking account of conformational equilibria. The conformer species are chosen so that they have minimal potential energies, the potential energy surface being estimated with a non-bonded interaction approximation. Excited state wave functions are improved by a model potential method. The ratio of the rotational strengths at 81 and 300 K, each of them being calculated as a statistical average of the rotational strengths of four conformers, is in good agreement with the corresponding observed value.
  • Hirotoshi Ito, Yasumasa J. I’Haya
    1976 Volume 49 Issue 12 Pages 3466-3471
    Published: 1976
    Released: April 19, 2006
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    Comments are given upon the approximate self-consistent renormalized RPA(SCrRPA) presented in our previous papar which assumes the correlated ground state wavefunction to be the linear combination of the Hartree-Fock ground state and doubly excited states, in the CI language. The rationalization of the approximate SCrRPA is made from the results computed by the complete SCrRPA, whose recipe is simply made. Finally, a numerical comparison of the several RPA methods is made as to the electronic spectra of four DNA bases by using the CNDO/S method.
  • Masahiro Harada, Yasushi Kai, Noritake Yasuoka, Nobutami Kasai
    1976 Volume 49 Issue 12 Pages 3472-3477
    Published: 1976
    Released: April 19, 2006
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    X-Ray crystal structure analyses of [PtCl2{(t-Bu)2P(CH2)2P(t-Bu)2}] (I) and [PtCl2{(t-Bu)2P(CH2)2P(t-Bu)2}, C6H5C1] (II) have been carried out. Crystals of I belong to monoclinic system: a=20.595(3), b=7.917(3), c=14.885(2) Å, β=109.03(1)°, space group P21/c with Z=4. II forms monoclinic crystals, P21/c: a=14.873(2), b=13.193(2), c=15.314(2) Å, β=98.75(1)°, Z=4. Both structures, solved by the heavy-atom method, have been refined anisotropically by least-squares procedure to R=0.067 and 0.078 for I and II respectively. There is no essential difference between the structures of [PtCl2{(t-Bu)2P(CH2)2P(t-Bu)2}] molecules in I and II. The coordination around the platinum atom is square-planar; Pt–P=2.262(3) and 2.265(3) Å and Pt–Cl=2.374(4) and 2.365(4) Å. The molecule has a pseudo-C2 symmetry: the platinum atom and the center of the C–C bond in the P–C–C–P lie on this pseudo-C2 axis.
  • Yoshikane Kawasaki, Mitsutoshi Aritomi, Jun Iyoda
    1976 Volume 49 Issue 12 Pages 3478-3482
    Published: 1976
    Released: April 19, 2006
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    Proton and carbon-13 nuclear magnetic resonance spectra and Raman spectra of some methylmercury compounds, CH3HgX, were measured. The spin-spin coupling constants, 2J(199Hg–H) and 1J(13C–H) of methylmercury nitrate in some strong acids were found to increase when the proton resonance of the methyl group attached to the mercury shifts to lower magnetic field. It was also found that the C–H stretching bands of the methyl group shift to higher frequency in the strong acids. The results are explained by an increase of the effective positive charge on the mercury. As has been observed in other alkylmercury compounds, the spin-spin coupling constant between directly bonded mercury and carbon nuclei, 1J(199Hg–C),of some methylmercury compounds in organic solvents increased with the geminal spin-spin coupling constant, 2J(199Hg–H). The 1J(199Hg–13C) value of methylmercury nitrate in strong acids was found to decrease, whereas the 2J(199Hg–H) values increased in these media. The lowering of the mercury-carbon bond strengths in the strong acids, which was revealed from the mercury-carbon stretching frequency in the Raman spectra, is considered one possible reason for the decrease of the 1J(199Hg–13C) value.
  • Hideo Takeuchi, Jean-Luc Bribes, Issei Harada, Takehiko Shimanouchi
    1976 Volume 49 Issue 12 Pages 3483-3492
    Published: 1976
    Released: April 19, 2006
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    Normal coordinate treatments of the crystal vibrations of methyl chloride, methyl bromide, methyl iodide, and their perdeuterated analogs have been made. The values of force constants of non-bonded atom interactions have been determined so as to give the best fit to the lattice frequencies and the splitting frequencies of the intramolecular vibrations. It has been found that the dipole-dipole interactions are essential to account for the splittings of some internal modes, but their effects on lattice frequencies are negligible.
  • Minoru Ohki, Akio Takenaka, Hirotaka Shimanouchi, Yoshio Sasada
    1976 Volume 49 Issue 12 Pages 3493-3497
    Published: 1976
    Released: April 19, 2006
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    The complex crystals of 5-bromocytosine and N-tosyl-L-glutamic acid were obtained from their aqueous solution. The space group is P1 with dimensions of a=10.843(1), b=11.690(2), c=10.879(2) Å, α=122.15(1), β=121.38(1), γ=69.93(1)°, and Z=2. The structure was solved by the heavy atom method and refined by a block-diagonal least-squares method. The undissociated γ-carboxyl group of glutamic acid is bound with O(2) and N(4) of 5-bromocytosine through hydrogen bonds. This interaction mode is different from those found in some cytosine : glycine complexes and cytidine : N-benzyloxycarbonyl-L-glutamic acid complex dihydrate in which the dissociated α-carboxyl group plays a role. This is the first example of interaction between cytosine and the acidic side group of amino acid.
  • Hiroyuki Nishide, Jichio Deguchi, Eishun Tsuchida
    1976 Volume 49 Issue 12 Pages 3498-3501
    Published: 1976
    Released: April 19, 2006
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    Poly(4-vinylpyridine) was crosslinked with 1,4-dibromobutane, The obtained resin (DBQP) formed a stable complex with Cu2+, and the adsorption capacity of DBQP varied with the degree of crosslinking. The complex, formation of DBQP with Cu2+ was studied by examining the adsorption equilibrium and the spectroscopic measurement. The resin complex seems to be formed via no step-by-step mechanism, and the stability constant was appreciably large in comparison with those of non-crosslinked polymers and of a monomeric analogue. In the highfy crosslinked resins, the ligand-field is relatively weak and the stability of the Cu2+ complex is decreased.
  • Tamaichi Ashida, Suteo Iwata, Takashi Yamane, Masao Kakudo, Akira Take ...
    1976 Volume 49 Issue 12 Pages 3502-3508
    Published: 1976
    Released: April 19, 2006
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    The crystal structures of two Schiff base complexes, bis[N-(3-methoxysalicylidene)isopropylaminato]nickel (II) and -cobalt(II), have been determined. Ni complex: brown, room temperature phase, monoclinic, P21/c, a=21.089, b=7.254, c=14.386 Å, β=98.40°, Z=4, final R=0.076. Co complex: red, triclinic, P\bar1, a=22.699, b=7.395, c=14.099 Å, α=107.78, β=99.03, γ=93.75°, Z=4, final R=0.13. In both crystals the metal ions have distorted tetrahedral coordinations. The two crystals are roughly isostructural, although appreciable differences exist in both of the molecular and crystal structures. The Co complex gives a unique example of the methoxy group which sticks out nearly perpendicularly from the phenyl plane.
  • Yuki Fujii, Takashi Isago, Mitsuo Sano, Noriko Yanagibashi, Shigeru Hi ...
    1976 Volume 49 Issue 12 Pages 3509-3517
    Published: 1976
    Released: April 19, 2006
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    Two series of new mixed ligand cobalt (III) complexes with the general formulas of [Co(sal2en)(L-aa)] and [Co(7,7′-Me-sal2en)(L-aa)] (where L-aa=anion of L-ala, L-val, L-leu, L-isoleu, L-met, L-thr, L-phe, L-tyr, or L-trp) have been prepared and characterized. All are labile for both isomerization and substitution reactions and each exists in an equilibrium mixture of ΛL- and ΔL-cis1(fac)-isomers (ΛL>ΔL)in methanol. The isomer’s ratios, ΛL/ΔL were estimated from their PMR spectra, and the following facts were found: The increasing order of the ratios is L-ala∼L-met∼L-leu<L-val<L-isoleu<L-thr<L-phe∼L-tyr<L-trp, and the ratios are larger in 7,7′-Me-sal2en-complexes than in sal2en-complexes for each amino acid.
  • Toyokichi Kitagawa, Kazuo Nomura
    1976 Volume 49 Issue 12 Pages 3518-3523
    Published: 1976
    Released: April 19, 2006
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    The electrochemical behavior of the cadmium(II) ion in the presence of 2-carboxy-1-pyrrolidinecarbodithioic acid (H2cpcd) as a chelating agent was investigated in an alkaline medium by d.c. polarography, a.c. polarography, cyclic voltammetry, and chronopotentiometry. The cadmium(II) chelate gave a reversible two-electron reduction wave at −0.86 V vs. SCE, with a postwave at −0.95 V. From the dependence of the total wave height on the mercury column height and from the methods of cyclic voltammetry, the electrode reduction of the cadmium(II) chelate was found to be diffusion-controlled. The diffusion current constant was 2.42 μA mol−1 m3 mg−2⁄3 s1⁄2. The postwave was identified as an adsorption wave of the cadmium(II) chelate from the dependence of the postwave height on the mercury column height, the a.c. peak height, the electrocapillary curves, and the results of chronopotentiometry. The surface excess of cadmium(II) chelate adsorbed on the mercury electrode was evaluated by means of three different electrochemical techniques. The composition of the cadmium(II)–cpcd chelate in the presence of excess H2cpcd was Cd(cpcd)22−, and the overall stability constant was estimated to be 8.0×1012 at 25.0 °C and μ=1.5.
  • Etsuro Kobayashi
    1976 Volume 49 Issue 12 Pages 3524-3529
    Published: 1976
    Released: April 19, 2006
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    The method for synthesis of N4P4(NH2)8 by the reaction between (NPCl2)4 and ammonia and its hydrolysis behavior were investigated. The reaction of (NPCl2)4 with liquid ammonia took place violently at first, and the resulting product contained more than several percents of an insoluble material. The extract from this product had a rather low yield, about 20–25%. However, such a drastic reaction could be avoided by the addition of a small amount of dioxane to the reaction system; then the insoluble material did not form, and the yield increased to 55–66%. The final product contained P 37–38% and N 50–51%; thus the mole ratio of N to P was exactly 3 : 1 and the composition agreed with that of N4P4(NH2)8·H2O. When an aqueous solution of N4P4(NH2)8 was refluxed at 100 °C, the compound was initially hydrolyzed to PO(NH2)3 and P2O2NH(NH3)4, these being converted into PO(ONa)(NH2)2. At room temperature, the rate of hydrolysis was quite slow, but the composition of the hydrolysis products was similar to that at 100 °C. In a sodium hydroxide solution, N4P4(NH2)8 was converted directly into PO(ONa)(NH2)2 at an elevated temperature. The rate of the alkali hydrolysis obeyed a first-order equation, with the rate constants of 1.0×10−3, 2.5×10−3, 1.9×10−2, and 4.2×10−2 at 50, 60, 80, and 90 °C, respectively. These values were about 2.7 times that of N3P3(NH2)6. The activation energy of the reaction was 20.8 kcal/mol. The acid hydrolysis behavior resembled that in the neutral hydrolysis, but the reaction was accelerated with acid strength. The formation of tetrametaphosphimate by the hydrolysis of N4P4(NH2)8, that had previously been claimed, could not be reproduced in this study.
  • Masao Uetsuki, Yuzuru Fujiwara
    1976 Volume 49 Issue 12 Pages 3530-3539
    Published: 1976
    Released: April 19, 2006
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    Structural investigation was carried out by means of 1H-NMR, ESR, and chemical ionization mass spectrometry on the complexes formed by the reaction of alkylaluminum with titanium(IV) t-butoxide or vanadium(IV) t-butoxide as a catalyst for polymerization of isoprene. The t-butoxide was monomeric in benzene, and reduced to form a bivalent complex via trivalent ones on addition of the alkylaluminum to the solution followed by the formation of two kinds of binuclear aluminum complexes. In the trivalent state the complexes caused polymerization of isoprene to form five kinds of polymers, 1,4-polymerization of isoprene being likely caused by tris[di-μ-t-butoxo-dialkyltitanium(III)]aluminum, or the corresponding vanadium(III) complex. The final product of the reduction of vanadium(IV) t-butoxide was bis(di-μ-alkyl-dialkylaluminum)vanadium(II), which exhibits no catalytic activity.
  • Yukihiro Yamamoto, Sumio Kaizaki, Yoichi Shimura
    1976 Volume 49 Issue 12 Pages 3540-3543
    Published: 1976
    Released: April 19, 2006
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    Three geometrical isomers of fac(ida)-[Co(NO2)(gly)(ida)] have been prepared and optically resolved (gly=glycinato(1–) and ida=iminodiacetato(2–) ligand), and their configurations were determined from the visible and ultraviolet absorption, and circular dichroism spectra. A diastereomeric pair was obtained for the corresponding L-alaninato, L-serinato, or L-prolinato complex.
  • Fumio Kinomura, Tadashi Tamura, Iwao Watanabe, Yu Yokoyama, Shigero Ik ...
    1976 Volume 49 Issue 12 Pages 3544-3547
    Published: 1976
    Released: April 19, 2006
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    Binding energies of core electrons in Cr(C6H6)2, Cr(C6H6)(CO)3, and Cr(CO)6 were measured by means of X-ray photoelectron spectroscopic method in solid phase. By comparison with their UPS spectra observed in gasous phase, binding energies referred to vacuum level can be obtained. On the basis of this result, charge distribution in these complexes are estimated. The intramolecular relaxation energy of Cr(C6H6)2 is also discussed.
  • Izumi Nakai, Tetsuo Shima, Mihoko Izawa, Kozo Nagashima
    1976 Volume 49 Issue 12 Pages 3548-3551
    Published: 1976
    Released: April 19, 2006
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    Some varieties of zircon which contain yttrium, niobium, and phosphorus in solid solution have been synthesized at temperatures 500–550 °C and under pressures 700–1000 kg/cm2. In zircon containing yttrium, the unit cell constants a and c increase with increase in yttrium content up to 70 mol%. From IR and TGA studies, a valence compensation accompanying the substitution of yttrium is assumed to be effected by a concomitant substitution of OH for O sites, and the variety is represented by a formula (Zr,Y)Si(O,OH)4. On the other hand, the substitution of Nb5+ for Zr4+ is followed by a decrease in the cell constants. Zircon phase did not form from starting materials with more than 20 mol% of niobium content. From the syntheses of zircon containing both yttrium and niobium, the formula (Zr,Y,Nb) Si(O,OH)4 is found to be appropriate for naegite. An attempt was made to synthesize some solid solutions between zircon and xenotime. The unit cell constant c of the products is found to decrease with the substitution of PO4 for SiO4.
  • Osamu Makabe, Jutaro Yajima, Sumio Umezawa
    1976 Volume 49 Issue 12 Pages 3552-3557
    Published: 1976
    Released: April 19, 2006
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    Several D-arabino- and 2′-deoxy-D-ribonucleosides of carbamoylpyrazoles were synthesized by an acid-catalyzed fusion reaction of 1-O-acetyl derivatives of the corresponding sugars with pyrazole derivatives. Spectral evidences for their N-glycosylation sites and anomeric configurations were presented.
  • Kazuyoshi Seguchi, Akira Sera, Kazuhiro Maruyama
    1976 Volume 49 Issue 12 Pages 3558-3563
    Published: 1976
    Released: April 19, 2006
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    The Diels-Alder reactions of polychlorocyclopentadienes with substituted ethylenes were investigated, and the rates of the reaction and the endo : exo adduct distributions were determined. The introduction of a chlorine atom at the C5 position of cyclopentadiene resulted in an enhanced endo preference for substituents in the adducts, despite the depressed reactivity of the diene. This is contrary to what is to be expected from the so-called “selectivity-reactivity relationship in the Diels-Alder reaction.” The results in this work were explained in terms of steric interaction between the C5-chlorine atom of the diene and the substituent of dienophiles.
  • Daisuke Takaoka, Keiko Watanabe, Mitsuru Hiroi
    1976 Volume 49 Issue 12 Pages 3564-3566
    Published: 1976
    Released: April 19, 2006
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    From the leaves of Machilus japonica Sieb. et Zucc., four lignans were isolated; they have been found to be (+)-galbacin [1], (+)-galbelgin [2], (−)-licarin-B [4], and a new lignan, machilusin, whose structure can be described as [3a] or [3b].
  • Jyuzo Nakayama, Kazuo Fujiwara, Masamatsu Hoshino
    1976 Volume 49 Issue 12 Pages 3567-3573
    Published: 1976
    Released: April 19, 2006
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    Various salts of 1,3-benzodithiolylium ion were prepared in excellent yields on treatment of 2-alkoxy- and 2-alkylthio-1,3-benzodithioles with acids in acetic anhydride. The reactions of 1,3-benzodithiolylium tetrafluoroborate (1a) with a wide variety of nucleophilic reagents (alcohols, water, thiols, hydrogen sulfide, primary, secondary, and tertiary amines, ammonia, N,N-dimethylformamide, electron-rich aromatic compounds, active methylene compounds, tropilidene, and sodium borohydride) were studied. In all cases examined, 1a reacted with nucleophilic reagents at the 2-position to give the corresponding 1,3-benzodithioles in good yields, excepting the reactions with tertiary amines and N,N-dimethylformamide which resulted in the formation of dibenzotetrathiafulvalene. Salt 1a was also prepared from 1,3-benzodithiole and trityl tetrafluoroborate.
  • Akira Oku, Takamasa Suzuki, Hajime Koura, Fujio Mashio
    1976 Volume 49 Issue 12 Pages 3574-3577
    Published: 1976
    Released: April 19, 2006
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    Phenylcarbamoyl cyanide (1), under thermal conditions or base-catalysis, behaves as a source of bothphenyl isocyanate and hydrogen cyanide in the syntheses of carbamates, cyanohydrins, and iminohydantoins. The reaction mechanism of 1 with methanol in the presence of tertiary amine was investigated. The following observations (i–iii) led us to deduce that phenyl isocyanate was not involved as the intermediate and that the rate-determining step involves nucleophilic displacement of 1 by the alkoxyl group, reinforced by the base: (i) the N–H exchange was too fast to be rate-determining; (ii) d-labelling experiments showed kH/kD=1.8–1.9 in any of the reactions, 1-d1+MeOH, 1-d0+MeOD, and 1-d1+MeOD, and (iii) diphenylcarbamoyl cyanide reacted only 7.2 times slower than did 1.
  • Tatsuzo Ishigami, Tomoji Murata, Tadashi Endo
    1976 Volume 49 Issue 12 Pages 3578-3583
    Published: 1976
    Released: April 19, 2006
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    The solution photodimerization of methyl (E)-p-nitrocinnamate has been studied under various conditions. Cis and trans dimers of head-to-head configuration were formed predominantly, the ratio of the dimers being highly dependent on the concentration and the solvent. The sensitization, the quenching phenomena, and the external heavy-atom effect were observed in this photodimerization. It appears likely that the excited multiplicity responsible for the formation of the trans-dimer is the triplet π,π* state and that both the singlet and the triplet π,π* states contribute to the production of the cis-dimer.
  • Akihisa Sakumoto, Teijiro Miyata, Masamitsu Washino
    1976 Volume 49 Issue 12 Pages 3584-3588
    Published: 1976
    Released: April 19, 2006
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    The competitive addition of sodium hydrogensulfite to allyl and 2-methylallyl alcohols was investigated at the pH range from 3 to 5. The relative reactivity of allyl alcohol to 2-methylallyl alcohol decreased with increasing pH. Sulfite radical ion was mainly participating in the addition at pH 5, and hydrogensulfite radical at pH 3. From the kinetic analysis of the pH dependence, the ratio of reactivities of allyl alcohol and 2-methylallyl alcohol toward sulfite radical ion was 0.213, and the same ratio toward hydrogensulfite radical was 0.305. Further, the ratio of reactivities of hydrogensulfite radical and sulfite radical ion toward allyl alcohol was 1.32, and the same ratio toward 2-methylallyl alcohol was 0.927. The dissociation constant of hydrogensulfite radical was the order of 3×10−5(pKa=4.5).
  • Shigeru Mihara, Fumio Shimizu, Seiji Miyamoto
    1976 Volume 49 Issue 12 Pages 3589-3593
    Published: 1976
    Released: April 19, 2006
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    Syntheses are described of three protected peptide fragments which correspond to positions 1–6, 7–11, and 12–22, respectively, of the entire amino acid sequence of porcine motilin, a gastric motoractivity-promoting polypeptide. Stable tosyl group was used for the protection of ε-amino group of lysine and guanidino group of arginine. These protected peptide fragments were mainly constructed in step wise manner using benzyloxycarbonyl amino acid by mixed anhydride method in the presence of N-hydroxysuccinimide. For preparation of the C-terminal undecapeptide, fragment condensation method was employed using two protected tripeptide azides. The protected peptides and intermediates could be readily purified by simple procedure.
  • Fumio Shimizu, Kenichi Imagawa, Shigeru Mihara, Noboru Yanaihara
    1976 Volume 49 Issue 12 Pages 3594-3596
    Published: 1976
    Released: April 19, 2006
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    Synthesis of porcine motilin is described. Construction of the entire molecule of this hormone was carried out by the fragment condensation method in solution employing Rudinger’s azide modification, and the resulting protected docosapeptide was deblocked by sodium–liquid ammonia procedure. Purification of the final product was performed by ion exchange chromatography on CM-Sephadex using ammonium acetate as eluent and gel filtration on BiO–Gel P-6. Purity of the synthetic docosapeptide was assessed by TLC in two different solvent systems and amino acid analysis. This polypeptide showed gastric motoractivity stimulating action on 30 min intravenous infusion in dogs in 5 ng/kg/min doses, which is characteristic to porcine motilin.
  • Masakazu Yamashita, Yoshihisa Watanabe, Take-aki Mitsudo, Yoshinobu Ta ...
    1976 Volume 49 Issue 12 Pages 3597-3600
    Published: 1976
    Released: April 19, 2006
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    Disodium tetracarbonylferrate (–II) is an efficient catalyst for the dismutation of aromatic aldehydes to esters, 2RCHO→RCOOCH2R. Aliphatic ones give aldol-condensation products upon treatment with the ferrate. A successive reaction of the ferrate with an aldehyde, RCHO, and then with alkyl iodide, R’I, gives an ester, R’COOCH2R, after protonation. The mechanisms of these reactions are discussed.
  • Hiroshi Minato, Kentaro Okuma, Michio Kobayashi
    1976 Volume 49 Issue 12 Pages 3601-3604
    Published: 1976
    Released: April 19, 2006
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    Ethoxydimorpholinosulfonium tetrafluoroborate and tetraphenylborate were prepared by ethylation of dimorpholino sulfoxide. They were readily hydrolyzed with water but did not react with methanol. In the reactions with nucleophiles, they acted as ethylating agent for β-picoline, triethylamine, diethylamine, methoxide ion, and chloride ion. When dimorpholino sulfide, 1-chlorobenzotriazole, and an alcohol were allowed to react at −80 °C, the main products were an alkyl chloride, dimorpholino sulfoxide, and morpholinium chloride. Alkoxydimorpholinosulfonium chloride was presumed to be the intermediate, which decomposed by an SN2-type nucleophilic attack of chloride ion on the alkyl group. When (+)-2-octanol was used, the 2-chlorooctane formed was of almost completely inverted configuration (enantiomeric excess, 97%). The yield of alkyl chlorides decreased in the order of methyl (80%), isopropyl (51), and t-butyl (20).
  • Toshio Kobayashi, Kimiaki Imafuku, Hisashi Matsumura
    1976 Volume 49 Issue 12 Pages 3605-3606
    Published: 1976
    Released: April 19, 2006
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    The dissociation constants of various 5-styryl-2-aminotropones were determined spectrophotometrically using 50%(v/v) aqueous methanol and correlated by the use of Hammett equation, with ρ=0.57.
  • Toshio Fuchigami, Keijiro Odo
    1976 Volume 49 Issue 12 Pages 3607-3610
    Published: 1976
    Released: April 19, 2006
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    A new, efficient method for the preparation of 1,2,4-oxadiazoles from N-benzoylamidino compounds by treatment with t-butyl hypochlorite and sodium hydroxide has been devised. It was supposed that the ring formation proceeds via a nitrene intermediate.
  • Shoichi Kusumoto, Shinichi Tsuji, Keiyuu Shima, Tetsuo Shiba
    1976 Volume 49 Issue 12 Pages 3611-3614
    Published: 1976
    Released: April 19, 2006
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    An alternative total synthesis of streptolidine (roseonine, geamine) was achieved starting from D-xylose. Direct azidolysis of methyl 2,3,5-tri-O-mesyl-α-D-xylofuranoside (6a) afforded methyl 2,3,5-triazido-2,3,5-trideoxy-α-D-arabinofuranoside (9a), whereas the β-anomer of 6a gave only 3,5-diazido-3,5-dideoxy-2-O-mesyl-β-D-ribofuranoside (8b) indicating that the glycosidic configuration in the furanoside system has a decisive influence on the reactivity of the 2-mesyloxy group. However, the β-anomer of diazide (8b) was anomerized to α-anomer which readily undergoes azidolysis to give the triazide (9a). The triazide was successively hydrogenated, benzyloxycarbonylated, and then hydrolyzed to give 2,3,5-tris(benzyloxycarbonylamino)-2,3,5-trideoxy-D-arabinofuranose, which was identical with that prepared from D-ribose. Streptolidine could be synthesized from this key intermediate.
  • Ken Inouye, Fusako Shinozaki, Makoto Kanayama, Hideo Otsuka
    1976 Volume 49 Issue 12 Pages 3615-3619
    Published: 1976
    Released: April 19, 2006
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    The final coupling, deprotection and purification processes for the synthesis of octadecapeptides, H–Ser–Tyr–Ser–Met–Glu–His–Phe–Arg–Trp–Gly–Lys–Pro–Val–Gly–Lys–Lys–Arg–Arg–OH(I) and H–Ser–Tyr–Ser–Met–Glu–His–Phe–Arg–Trp–Gly–Lys–Pro–Val–Gly–Lys–Lys–Arg–Arg–NH2 (II), corresponding to the first eighteen amino acid residues of corticotropin (ACTH) are described, in which the N-hydroxysuccinimide ester of the N-terminal decapeptide derivative is coupled with the C-terminal octapeptide and octapeptide amide derivatives to give the two protected end products. The same decapeptide active ester is also utilized to the synthesis of a nonadecapeptide, H–Ser–Tyr–Ser–Met–Glu–His–Phe–Arg–Trp–Gly–Lys–Pro–Val–Gly–Lys–Lys–Arg–Arg–Pro–NH2 (III), identical with the first nineteen amino acid residues of ACTH. The in vivo steroidogenic potencies of the synthetic peptides are compared with that of the synthetic human ACTH (αh-ACTH) as reference to show that the relative potencies of I, II, and III vs. αh-ACTH are 0.14, 0.48, and 0.47, respectively, as estimated on a molar basis.
  • Ken Inouye, Yoshie Sumitomo, Masaru Shin
    1976 Volume 49 Issue 12 Pages 3620-3628
    Published: 1976
    Released: April 19, 2006
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    The syntheses are described of a hexacosapeptide H–Ser–Tyr–Ser–Met–Glu–His–Phe–Arg–Trp–Gly–Lys–Pro–Val–Gly–Lys–Lys–Arg–Arg–Pro–Val–Lys–Val–Tyr–Pro–Asn–Gly–OH (I) and a heptacosapeptide H–Ser–Tyr–Ser–Met–Glu–His–Phe–Arg–Trp–Gly–Lys–Pro–Val–Gly–Lys–Lys–Arg–Arg–Pro–Val–Lys–Val–Tyr–Pro–Asn–Gly–Ala–OH (II) corresponding to the first twenty-six and twenty-seven amino acid residues, respectively, of corticotropin (ACTH), in which a new protecting group 1-methylcyclohexyloxycarbonyl (Mhoc) is utilized for the temporary protection of the ε-amino function of lysines. The in vivo steroidogenic potencies of the synthetic peptides I and II are compared on a molar basis with those of ACTH(1–18)-NH2 and synthetic human ACTH (αh-ACTH) to demonstrate that the relative potencies of I and II vs. ACTH(1–18)–NH2 are 2.3 and 2.3–3.8, respectively, and those vs. αh-ACTH are 1.1 and 1.1–1.8, respectively.
  • Hajime Matsushita, Yasuko Tsujino, Masao Noguchi, Sadao Yoshikawa
    1976 Volume 49 Issue 12 Pages 3629-3632
    Published: 1976
    Released: April 19, 2006
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    The degree of the optical activations of racemic α-substituted carbonyl compounds via the formation of optically active immonium salts and the subsequent hydrolysis were largely affected by acids used for the hydrolysis of the enamines. The ratio of the diastereomeric immonium salts depends on the temperature. There is a relationship between the configuration of the optically activated carbonyl compounds and those of amines used. These suggest that the optical activation is due to the asymmetric transformation.
  • Yukito Murakami, Yasuhiro Aoyama, Kazuyuki Dobashi, Masaaki Kida
    1976 Volume 49 Issue 12 Pages 3633-3636
    Published: 1976
    Released: April 19, 2006
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    The catalytic functions of 10-oxo[20]paracyclophanyl-22(23)-methyltrimethylammonium chloride (1) in the hydrolysis and aminolysis reactions of p-nitrophenyl hexadecanoate (PNPP) were investigated in 1%(v/v)methanol–1%(v/v)dioxane-water over the pH 9–10 region at 40.0 °C and μ=0.2 (NaCl) with the initial PNPP concentration of 1.00×10−5 M. The paracyclophane (0.88×10−5 M) accelerated the hydrolysis of PNPP by one order of magnitude at pH 9.7. The presence of either ethanolamine or glycine in the 1-catalyzed deacylation of PNPP resulted in further rate enhancement. The rate enhancement was brought about by the aminolysis reaction of PNPP with the amines as confirmed by the product analysis. The greater reactivity of glycine relative to that of ethanolamine was attributed to the electrostatic interaction between the anionic carboxylate group of glycine and the cationic ammonium group of 1. The novel electrostatic-hydrophobic double-field catalysis was discussed for the glycinolysis reaction.
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