Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 50 , Issue 6
Showing 1-50 articles out of 71 articles from the selected issue
  • Yoko Suyama, Akio Kato
    1977 Volume 50 Issue 6 Pages 1361-1366
    Published: 1977
    Released: April 19, 2006
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    The solid-state reactions between CVD–TiO2 powders of anatase- and rutile-forms with various particle sizes and BaCO3 were investigated in O2 and CO2. The reactivity of the TiO2 powders and the apparent activation energy for the reaction were independent of the crystal type of TiO2. The reactivity of the TiO2 powders increased remarkably as the particle sizes grew smaller than 0.15 μm. When such fine CVD–TiO2 powders were used, the reaction proceeded to completion at temperatures below 1000 °C in both O2 and CO2 and gave fine BaTiO3 powders. The particles of BaTiO3 produced appeared single-crystalline and kept a shape similar to that of the starting TiO2 particle. The sizes of the BaTiO3 particles were controlled by those of the starting TiO2 and were independent of those of BaCO3.
  • Yoshihiko Kambara, Hiroshi Yoshida
    1977 Volume 50 Issue 6 Pages 1367-1371
    Published: 1977
    Released: April 19, 2006
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    Electron spin resonance was examined during the continuous photolysis of a flowing solution of p-benzoquinone in ethanol at room temperature. It was found that both semiquinone anions and semiquinone radicals were generated, but their relative yields changed depending on the experimental conditions. The semiquinone anion was generated in a comparatively high yield at low concentrations of p-benzoquinone and at high flowing rates. Its formation was, however, quenched by the addition of acetic acid without transformation to the semiquinone radical. The semiquinone radical was generated efficiently at high p-benzoquinone concentrations and at low flowing rates. Its formation was enhanced by the addition of hydroquinone. These results, as well as the previous results on the effect of the wavelength of light, indicate, in contrast with the currently accepted view, that there is effectively no equilibrium in ethanol between the semiquinone radical and the semiquinone anion under the present experimental conditions, and that the latter is formed by a photoinduced one-electron transfer from solvent to p-benzoquinone. The semiquinone radical seems to arise from the hydrogen abstraction of excited p-benzoquinone from the hydroquinone formed as a product during photolysis.
  • Toshio Yoshioka
    1977 Volume 50 Issue 6 Pages 1372-1378
    Published: 1977
    Released: April 19, 2006
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    The static magnetic susceptibility, and ESR and proton NMR spectra of powder samples of monochloroporphyrexide were measured above 1 K and compared with those of porphyrexide. A broad maximum in the static susceptibility of monochloroporphyrexide, indicating an antiferromagnetic interaction, appeared at 22.5 K. The relative susceptibilities of the two radicals obtained from the ESR signal intensities and the proton NMR shifts agree qualitatively with the static susceptibilities. In the low-field ESR spectra (135 MHz) of each radical, broadening of the g=2 absorption line and distinct appearance of the g=4 absorption line were found in the temperature region below Tm, the temperature at which the susceptibility is maximum. The anisotropy of the g-value was estimated from Q-band ESR spectra. Furthermore, the unpaired electron-spin distribution over the ring was estimated from the X-band ESR and the proton NMR spectra. The results are interpreted assuming that the magnetic behavior of the two radicals is due to alternating antiferromagnetic Heisenberg linear chains with alternating parameters, a=0.4 and a=0.6, respectively.
  • Yoshitsugu Oono, Yukio Nishimura
    1977 Volume 50 Issue 6 Pages 1379-1381
    Published: 1977
    Released: April 19, 2006
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    Empirical linear relations between the square roots of the electron-scattering cross sections for molecules and the cube roots of the van der Waals volumes for molecules due to Bondi are shown. The relations allow one to estimate, for example, the electron-impact ionization cross sections at 75 eV to within an error of ±15%. A dimensional analytic explanation of the relations is given.
  • Takako Shinoda
    1977 Volume 50 Issue 6 Pages 1382-1385
    Published: 1977
    Released: April 19, 2006
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    Laser Raman spectra of tetramethylsilane in its three crystalline forms and in the liquid state have been observed for the lattice and intramolecular vibrational regions. The bands due to lattice vibrations increase as the transitions from α to β and to γ occur. The spectra of the β and γ forms exhibit crystal-field splittings of intramolecular bands. The observed spectra suggest that the β and γ forms are isomorphous with each other and the α form has a higher symmetry.
  • Shozo Yanagida, Kazutomo Takahashi, Mitsuo Okahara
    1977 Volume 50 Issue 6 Pages 1386-1390
    Published: 1977
    Released: April 19, 2006
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    The reaction of noncyclic poly(oxyethylene) derivatives with alkali and alkaline earth metal ions was investigated by means of the solvent extraction of their thiocyanates or iodides. Polyethylene glycols with more than 23 oxyethylene units showed a strong extracting power comparable to those of the crown ethers, and the power increased with the increasing number of oxyethylene units in them. Extraction studies using homogeneous poly(oxyethylene) monododecyl ethers revealed that more than 7 oxyethylene units were necessary to bind the potassium ion in the water phase and to transfer the complexed salt to the organic phase, and that the extracting ability of octa(oxyethylene) monododecyl ether was about one sixth of that of 18-crown-6. The monododecyl ether is fairly effective as a complexing agent for potassium picrate even below its critical micelle concentration; the stoichiometry of the extractable complex was found to be 0.8:1 with respect to the ether and the picrate. There was no remarkable difference in the selectivity for alkali metal ions between noncyclic poly (oxyethylene) derivatives and 18-crown-6.
  • Kenichi Fukui, Kazuyoshi Tanaka
    1977 Volume 50 Issue 6 Pages 1391-1398
    Published: 1977
    Released: April 19, 2006
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    An interpretation is given on the characteristics of biradicaloids, such as the bonding, polar, and biradical characters of singlet biradicals. Systematization of the reactivity of singlet and triplet biradicals is based on the principle that 1) deformation takes place in the direction of bonding in singlet biradicals, and 2) deformation or bond formation occurs to separate unpaired-electrons from each other in triplet biradicals. Combination of the two principles is applied to the theory of orientation and stereoselection in excited-state reactions.
  • Tadayoshi Yoshida, Masataka Okuyama, Takahiro Itoh
    1977 Volume 50 Issue 6 Pages 1399-1402
    Published: 1977
    Released: April 19, 2006
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    A large, planar, bimolecular film (bilayer, 600 mm2) of cis-9-octadecenylamine (oleylamine) was found to be formed in an NiCl2 solution. From the effect of the added metal ions on the proton magnetic resonance spectrum of octadecenylamine, it appears that the complex between the octadecenylamine molecule and the metal ion increases the stability of the bilayer. The thickness of the bilayer depended strongly on the kind of solvent in the filmforming solution. When decane, a normal alkane solvent, was used, the thickness of the bilayer was greatest (4.6 nm), and the temperature effect was smallest. The experimental results are explained in terms of (i) the influence of the solvent on the conformation of the octadecenyl chain and (ii) the amount of solvent remaining in the film.
  • Shoichi Ikeda
    1977 Volume 50 Issue 6 Pages 1403-1408
    Published: 1977
    Released: April 19, 2006
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    A general method is developed to derive the Gibbs adsorption equation in the form applicable to aqueous solutions of electrolytes, either strong or weak, composed of multi-components. Assuming that the solution is ideal, the chemical potentials of solute electrolytes are represented by their concentrations, and the lowering of surface tension is calculated as a function of variations of these concentrations. Explicit expressions for surface excesses of various species are obtained on aqueous solutions of two strong electrolytes having a common cation, such as sodium dodecyl sulfate and NaCl, and on solutions containing a weak acid adjusted its ionization by addition of alkali, such as fatty acid or soap, in the presence of an added salt. The convention for drawing the Gibbs dividing plane is discussed when the Gibbs adsorption equation is represented in terms of all the species in solution.
  • Kiyoshi Okazaki, Masaki Yamabe, Shin Sato
    1977 Volume 50 Issue 6 Pages 1409-1415
    Published: 1977
    Released: April 19, 2006
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    The G-values for the ionization and excitation of thirty-eight gaseous compounds irradiated by 100 keV electrons have been calculated by combining the binary-encounter-collision theory with the theory of the degradation spectrum, which is based on the continuous-slowing-down approximation (CSDA). The thirty-eight compounds include C2–C6 alkanes, cycloalkanes, C2–C4 olefins, acetylene, 1,3-butadiene, benzene, toluene, phenol, pyrrole, furan, several alcohols, ethers, ketones, acetaldehyde, carbon dioxide, and hydrogen cyanide. Most of the calculated G-values of the electrons were in fair agreement with the experimental values. In the cases of several hydrocarbons, the dissociation from the superexcited state into the neutral fragments was taken into account, since the data for the fragmentation ratios were available. In the case of acetylene, the discrepancy in the G-values of electrons obtained experimentally and theoretically suggests that excited acetylene gives rise to a chemiionization reaction. In order to check the CSDA, the Fowler equation for helium has been calculated and the results compared with those obtained under the CSDA. The discrepancy in the G-values obtained by the two methods did not exceed 7%.
  • Kazuaki Harata
    1977 Volume 50 Issue 6 Pages 1416-1424
    Published: 1977
    Released: April 19, 2006
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    α-Cyclodextrin (α-CDx) forms a 1 : 1 complex with p-nitrophenol (p-NP) and p-hydroxybenzoic acid (p-HB). The crystal structures were determined by the X-ray method. The crystals of both complexes are orthorhombic, and the space group is P212121 with Z=4. The cell dimensions are a=13.455(1), b=15.296(1), and c=24.740(3) Å for the p-NP complex, and a=13.356(1), b=15.342(1), and c=24.896(2) Å for the p-HB complex. The crystal structures were determined on the basis of the isomorphous structure of the p-iodophenol complex by using 4811 reflections for the p-NP complex and 4692 reflections for the p-HB complex, and refined by the block-diagonal least-squares method to the final R-values of 0.066 and 0.067 respectively. In both complexes, the guest molecule is included in the α-CDx cavity, and the α-CDx ring is deformed from the regular hexagonal symmetry as a result of the inclusion of the planar molecule. The nitrophenyl or carboxyphenyl group is located in the cavity, while the phenolic hydroxyl group protrudes from the secondary hydroxyl side of the cavity. Several intermolecular hydrogen-hydrogen contacts shorter than the ideal van der Waals contact are observed between α-CDx and guest molecules, indicating that the guest molecule is rigidly fixed in the cavity. The nitro or carboxyl group is situated on the O(6) side and is hydrogen-bonded to water or a hydroxyl group of the adjacent α-CDx molecule. The geometry of the complex gives a reasonable model for the α-CDx-substrate complex in the hydrolysis of p-nitrophenyl acetate and p-carboxyphenyl acetate catalyzed by α-CDx.
  • Eiji Kubota, Masatoki Yokoi
    1977 Volume 50 Issue 6 Pages 1425-1430
    Published: 1977
    Released: April 19, 2006
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    Conductance data are reported for dilute solutions of pentaamminenitrocobalt(III) sulfate, [Co(NO2)(NH3)5]SO4, and tris(1,10-phenanthroline)iron(II) sulfate, [Fe(phen)3]SO4 in water–ethylene glycol mixed solvents at 25 °C. The conductance data were analyzed in terms of the 1957 Fuoss-Onsager and Fuoss-Hsia equations. While the application of the 1957 Fuoss-Onsager equation to [Fe(phen)3]SO4 data suggested a complete dissociation of the salt over the entire range of solvent compositions, the Fuoss-Hsia equation fitted the data better and yielded KA values which are in accord with the ion association theories. [Co(NO2)(NH3)5]SO4 had a higher association constant in the range of solvent composition studied (0 to 40% ethylene glycol) than the predictions of the ion association theories.
  • Tsuyoshi Arakawa, Mamoru Mizumoto, Yusaku Takita, Noboru Yamazoe, Tets ...
    1977 Volume 50 Issue 6 Pages 1431-1436
    Published: 1977
    Released: April 19, 2006
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    The catalytic NO reduction with NH3 over Cu(II) ion-exchanged zeolite was studied with special attention to the temperature dependence of catalytic activity which reaches maximum at ca. 120 °C. ESR study showed that in the catalytic system all the exchanged copper ions exist as Cu(II) up to ca. 120 °C, above which Cu(II) ions decrease with a rise in temperature. The reaction rates measured at 110 and 140 °C were found to show similar dependence on both NO and NH3 partial pressures, indicating that the reaction mechanism does not differ much. By lowering temperature the Cu(I) ions formed at higher temperatures were reoxidized to Cu(II), accompanied by N2O formation due to the disproportionation of NO. From the results and the IR spectroscopic data a reaction mechanism was proposed. It includes a step in which NO reacts with NH3 adsorbed to Cu(II) ions to give rise to the evolution of N2 and the reduction of Cu(II) ions, and steps in which Cu(II) ions are regenerated accompanying the evolution of N2+N2O.
  • Chikara Amano, Shizuo Fujiwara
    1977 Volume 50 Issue 6 Pages 1437-1440
    Published: 1977
    Released: April 19, 2006
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    Tervalent platinum complex ions have been observed by the electron spin resonance method upon γ-irradiation of both bivalent and quadrivalent complexes. From their g-values, the tervalent complex ions can be classified into two types, one axially symmetric and the other rhombic, the former having typical g-values of 2(g⁄⁄) and 2.4(g), and the latter a g1-value slightly lower than the free electron value of 2.0023. It has been shown by means of ligand field theory that both types have 5d7 low spin electron configuration. The hyperfine interaction due to 195Pt is one order of magnitude larger than that in cobalt complexes with 3d7 low spin configuration, indicating that the configuration interaction involving 6s-orbital is more important than that for 3d transition metal complexes involving 4s-orbital, and that 5d electrons penetrate deeply into inner shells, resulting in core polarizarion.
  • Nobutake Suzuki, Hiroshi Hotta
    1977 Volume 50 Issue 6 Pages 1441-1444
    Published: 1977
    Released: April 19, 2006
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    The radiation-induced decoloration of azo and anthraquinone dyes was studied in N2O-saturated aqueous solutions containing NCS. In the N2O-saturated solutions, the decoloration yield, G(–Dye), increased markedly upon the addition of NCS, which is an efficient scavenger of the OH radical—that is, from 1.46 up to 2.10 for Acid Red 265 and from 0.51 up to 1.51 for Acid Blue 40 upon the addition of 1 mM NCS. In the nitrogen-saturated solutions, however, the G(–Dye) decreased upon the addition of NCS. It is concluded that the increase in the G(–Dye) upon the addition of NCS in the N2O-saturated solutions is mainly attributable to the attack of the radical anion (NCS)2 on the ring structure of the dyes. This radical anion is formed through the following path: NCS+OH→NCS+OH and NCS+NCS\ ightleftarrows(NCS)2. At low NCS concentrations, the G(–Dye) decreased for Acid Red 265 and increased for Acid Blue 40. This may be attributable to the larger reactivity of (NCS)2 on Acid Blue 40 than on Acid Red 265.
  • Yôichi Iida
    1977 Volume 50 Issue 6 Pages 1445-1448
    Published: 1977
    Released: April 19, 2006
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    The electronic spectrum of solid ion radical salt is known to be different from the monomer spectrum of the radical ion and to show an intermolecular charge-transfer band in the low-energy region. In order to understand the character of this charge-transfer absorption, one-dimensional Hubbard model was applied to such solid ion radical salt. The transition energy and the theoretical line shape of the charge-transfer absorption were derived and were compared with those of certain TCNQ, anion radical salts.
  • Kaoru Suzuki, Kozo Kuchitsu
    1977 Volume 50 Issue 6 Pages 1449-1452
    Published: 1977
    Released: April 19, 2006
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    A flowing-afterglow method was applied to the formation of CN(B2Σ+) from CH3CN by impact of metastable argon atoms, Ar(3P2,0). Emission spectra of CN B2Σ+-X2Σ+ (violet band) were analyzed to estimate the energies distributed to the vibrational and rotational motions of CN(B2Σ+). In comparison with the CN(B2Σ+) produced from HCN under similar experimental conditions, relative populations in excited vibrational states are smaller. The effective rotational temperatures range from 5000±1000 K (v=0–2) to 2000±1500 K (v=5–10). An intensity anomaly caused by the rotational perturbation with A2II is used for estimating the ratio of the formation rates of CN B2Σ+ and A2Π, FB/FA, to be 0.19±0.05.
  • Yoshimi Ohtani, Masatoshi Fujimoto, Akihiko Yamagishi
    1977 Volume 50 Issue 6 Pages 1453-1459
    Published: 1977
    Released: April 19, 2006
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    Chlorotris(triphenylphosphine)rhodium (I) exists in benzene as RhCl(PPh3)3, a dimeric species [RhCl(PPh3)2]2 and a reaction intermediate RhCl(PPh3)2. The rates of oxidative addition and replacement reactions were examined in benzene. For the oxidative addition reaction, RhCl(PPh3)3, RhCl(PPh3)2, or [RhCl(PPh3)2]2+X1\oversetkadd\ ightleftarrowsProducts (X1=H2, O2, C2H4, CHCl=CCl2 CH3I), it was found that the reaction intermediate RhCl(PPh3)2 is most reactive, the degree of its reactivity depending largely on the reactants (X1). A significant enhancement of the rate (ksub>kadd) was observed for the ligand substitution reaction, RhClX1(PPh3)m+X2\oversetksub\ ightleftarrowsRhClX2(PPh3)n+X1 (m, n=3 or 2), where X1=H2 and X2=olefin and vice versa. The results are discussed in relation to the mechanism of hydrogenation.
  • Kunihiro Watanabe, Akio Fujiwara, Ky\={o}z\={o} Kawagaki
    1977 Volume 50 Issue 6 Pages 1460-1463
    Published: 1977
    Released: April 19, 2006
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    8-Quinolinethiol reacts with indium in the presence of acetic acid to give a yellow ternary complex. The complex, which has a greenish-yellow fluorescence with an emission maximum at 515 nm, can be extracted into chloroform at pH 2–4. In the ternary complex, the fluorescence intensity was about two times as large as that of the indium 8-quinolinethiolato complex containing no acetate ion. The fluorescence was stable for at least 1 h. By the use of a 0.2 μg/ml uranine solution as the setting reagent, 0–25 μg of indium in 10 ml of chloroform was determined. The coefficient of the variation was 3% for 12 μg of indium. The extractability of the ternary complex from 50 ml of an aqueous solution into 10 ml of chloroform was 99%. Iron, mercury, and silver, which interfere with the determination of indium, were masked with ascorbic acid, potassium iodide, and thiourea. Other interfering elements, including zinc, cadmium, gallium, nickel, palladium, cobalt, antimony, gold, copper, bismuth, and vanadium, must be removed before any analysis.
  • Shoichiro Yamada, Hideaki Tanaka, Kuniko Yamanouchi
    1977 Volume 50 Issue 6 Pages 1464-1468
    Published: 1977
    Released: April 19, 2006
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    Cobalt(II), nickel(II), and copper(II) complexes with N-(9-fluorenyl)salicylideneaminates (abbreviated as X-sal-fl) have been examined in relation to the effect of steric condition on the structure of the metal complexes. Compounds of the type M(X-sal-fl)2 and their pyridine adducts were isolated as crystals. Complexes of the type Cu(X-sal-fl)Cl were also obtained. Both in the solid state and in non-donor solvents, the complexes Co(X-sal-fl)2 have a tetrahedral configuration, and Ni(X-sal-fl)2 and Cu(X-sal-fl)2 have a square-planar configuration. Possible structures of the pyridine adducts are discussed. The results indicate that the steric hindrance caused by fluorenyl is greater than that by diphenylmethyl.
  • Atsushi Mizuike, Akira Iino
    1977 Volume 50 Issue 6 Pages 1469-1471
    Published: 1977
    Released: April 19, 2006
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    A procedure has been established for obtaining quantitative diffusion profiles by means of an ion microanalyzer in the narrow region within 1 μm of the glass surface. The interdiffusion of silver and sodium ions in Pyrex glass immersed in molten silver nitrate was studied as an example.
  • Haruo Matsui, Hitoshi Ohtaki
    1977 Volume 50 Issue 6 Pages 1472-1475
    Published: 1977
    Released: April 19, 2006
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    The hydrolytic reactions of cadmium(II) ions were studied at 25 °C in dioxane–water and methanol–water mixtures with varying compositions of the organic solvents, each mixture containing 3 mol dm−3 (Li)ClO4 as an ionic medium. Emf measurements were carried out over the range of the total cadmium(II) concentrations of 0.2 to 0.8 mol dm−3 in all the systems. Two complexes Cd2OH3+ and CdOH+ were found in the dioxane–water mixtures, but the latter complex was not detected in the methanol–water system. The formation constant of the Cd2OH3+ complex was slightly larger in the methanol–water mixtures than in the dioxane–water mixtures at the same mole-fraction concentration of the organic solvents.
  • Katsuhiko Miyoshi, Yasushige Kuroda, Hiroshi Okazaki, Hayami Yoneda
    1977 Volume 50 Issue 6 Pages 1476-1481
    Published: 1977
    Released: April 19, 2006
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    The influence of added sodium and potassium chloride, bromide, and sulfate was examined on the Pfeiffer effect of the [Co(phen)3]2+- and [Ni(phen)3]2+-d-cinchoH+ systems in water (phen=1,10-phenanthroline, and d-cinchoH+=dextro-cinchoninium ion). It was found that the added anions enhance the circular dichroism (CD) induced in the d-d transition region of [Co(phen)3]2+ and [Ni(phen)3]2+ ions, and that the CD-enhancing order is Br>Cl>SO42−/2. These findings were well interpreted in terms of reduced electrostatic repulsion between [Co(phen)3]2+ or [Ni(phen)3]2+ and d-cinchoH+ by the added anions, and of the resulting enhanced enantiomerization of these cationic complexes in favor of Δ-isomers in the presence of d-cinchoH+. Logarithm of the magnitude of the induced CD was found to be a linear function of logarithm of the total anion concentration in all the systems examined. This fact gives a strong support to the above interpretation, and suggests a close resemblance of these Pfeiffer-active systems to aqueous cationic surfactant solutions.
  • V. B. Mohankumar, B. T. Thaker, Rakesh K. Kohli, P. K. Bhattacharya
    1977 Volume 50 Issue 6 Pages 1482-1485
    Published: 1977
    Released: April 19, 2006
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    Reactions of aminoalkanols have been carried out with mixed and non-mixed bis(Schiff base) complexes of copper(II). In these reactions one of the ligands combines with the aminoalcohol forming a tridentate ligand, wheras another ligand is removed. From the resulting complexes the tendency to form the Schiff base is found to be in the order 2-hydroxybenzophenone≈2-hydroxy-1-naphthaldehyde>salicylaldehyde>2-hydroxyacetophenone. The complexes formed have been characterized by analytical, spectral, and magnetic studies.
  • S. C. Baghel, K. K. Choudhary, J. N. Gaur
    1977 Volume 50 Issue 6 Pages 1486-1488
    Published: 1977
    Released: April 19, 2006
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    Butanedioate and pentanedioate form 1 : 3 highest complexes separately with lead (II) in aqueous medium, three mixed complexes of these two ligands with the metal ion expected in solution being observed. The formation constants of mixed complexes have been evaluated on the basis of polarographic measurements by the method of Schaap and McMasters. The formation constants of the mixed complexes [Pb(X)(Y)]2−, [Pb(X)(Y)2]4−, and [Pb(X)2(Y)]4− are 3.57, 4.22, and 4.49 respectively in their logarithmic form at 303 K, where X2− and Y2− stand for butanedioate and pentanedioate ion, respectively. The statistically calculated values of logarithm of formation constants are 3.43, 4.43, and 4.49 in the above order. The small differences in the observed and calculated values may be due to electrostatic, steric etc. factors. The relative probability of the existence of these mixed complexes and also simple complexes has been explained.
  • D. S. Joardar, S. K. Mondal, K. Nag
    1977 Volume 50 Issue 6 Pages 1489-1491
    Published: 1977
    Released: April 19, 2006
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    The methyl ester of 2-amino-1-cyclopentene-1-carbodithioic acid (HE) acts both as an unidentate and a bidentate ligand. With Ni(II) and Pd(II) the deprotonated chelates of the ME2 type are obtained readily, the corresponding Pt(II) complex being obtained on the addition of an equivalent amount of alkali. In these compounds, bond formation takes place from the nitrogen and the sulfur atoms and there is strong delocalization in the chelate ring. Unidentate bonding behavior of the ligand is observed in the complexes Pt(HE)2Cl2 and Rh(HE)3Cl3, where the bonding takes place through the nitrogen atom only.
  • Mikio Miyake, Hiroshi Yoneyama, Hideo Tamura
    1977 Volume 50 Issue 6 Pages 1492-1496
    Published: 1977
    Released: April 19, 2006
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    Photocatalytic reductions of MnO4, Cr2O72−, and Fe3+ on illuminated rutile were demonstrated. The suitability of a method to analyze the reduction process of the photocatalytic reaction was discussed. It was concluded that a high utilization of light energy could not be expected for photocatalytic reactions because both bands of the semiconductor participated in the reaction. In such a case, the development of the photocatalvtic process into a photoelectrochemical cell has a great advantage from the point of view of energy utilization.
  • Kazuo Sasaki, Seiji Tao, Yoshio Hirano
    1977 Volume 50 Issue 6 Pages 1497-1501
    Published: 1977
    Released: April 19, 2006
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    The performance of a hot wire type thermal separation column in which many horizontal barriers of Teflon or copper plates are installed has been examined. At the optimum spacing of barrier plates, the quality factor defined by (2AL)barrier/(2AL)open exceeds 3. This means that a barrier column constructed properly has a performance equivalent to that of an open column of three times taller in height. Visualization of a stream line in the barrier assembly indicates that a helical transverse motion takes place in the space partitioned by two adjacent barrier plates.
  • Yukio Kubota, Robert F. Steiner
    1977 Volume 50 Issue 6 Pages 1502-1505
    Published: 1977
    Released: April 19, 2006
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    The rotational motions of various acridine dyes bound to DNA were investigated by the measurements of nanosecond fluorescence anisotropy. It was found that the total decay of fluorescence is a single exponential, whereas the decay of fluorescence anisotropy is a sum of an exponential function and a constant. The apparent values of the rotational relaxation time of the complexes calculated from anisotropy data range from 21 to 31 ns. The results are discussed by comparing with those obtained from the measurements of steady-state fluorescence depolarization.
  • Hideo Ueda, Jiro Tanaka
    1977 Volume 50 Issue 6 Pages 1506-1509
    Published: 1977
    Released: April 19, 2006
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    The crystal and molecular structure of dl-2-cis-4-trans-abscisic acid has been determined by the X-ray method. The crystal is monoclinic, P21/c, with lattice parameters a=6.316(1), b=33.575(3), c=7.607(1) Å, and β=118.42(1)°. The molecule has two independent conjugated systems forming respective planes which are orthogonal to each other. The molecules form a dimer by the hydrogen bonding and are connected by the other hydrogen bonding along the c-axis.
  • Masahiro Hayashi, Kiyoshi Yamauchi, Masayoshi Kinoshita
    1977 Volume 50 Issue 6 Pages 1510-1512
    Published: 1977
    Released: April 19, 2006
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    Dialkyl phosphites were found to be efficient alkylating agents for various nitrogen heterocyclic compounds, especially for imidazole analogs and pyridones, producing the corresponding N-alkyl derivatives.
  • Hajime Matsushita, Yasuko Tsujino, Masao Noguchi, Sadao Yoshikawa
    1977 Volume 50 Issue 6 Pages 1513-1516
    Published: 1977
    Released: April 19, 2006
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    Enammonium salt of 2-methyl-1-(β-methylstyryl)piperidine (1) was isolated for the first time and characterized. The enammonium salt, 2-methyl-1-(β-methylstyryl)piperidinium chloride (2), was found to change easily to the corresponding iminium salt, 2-methyl-1-(2-phenylpropylidene)piperidinium chloride (3), at room temperature. The structure of the salts derived from 1-(β-methylstyryl)piperidine (4), 2-methyl-1-(β-methyl-styryl)pyrrolidine (5), 1-(β-methylstyryl)pyrrolidine (6), 1-(2-methyl-1-propenyl)pyrrolidine (7), and 2-methyl-1-(2-methyl-1-propenyl)piperidine (8) were also examined.
  • Noboru Torimoto, Tadao Shingaki, Toshikazu Nagai
    1977 Volume 50 Issue 6 Pages 1517-1521
    Published: 1977
    Released: April 19, 2006
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    Ethoxycarbonyl nitrene, generated by the photolysis of ethyl azidoformate (I), was inserted preferentially into the α C–H bonds of acyclic ethers. Each of the reactions with acyclic ethers gave N-alkoxyurethane via a cleavage of the C–O bond, indicating that an O–N ylide is an intermediate of the nitrene reaction. Comparing sensitized photolysis with direct photolysis of I in ethers and in alcohols, it was found that the nitrene insertion into the α C–H bonds of ethers proceeds for both singlet and triplet and that the insertion into the β and γ C–H bonds of ethers and the O–H bonds of alcohols proceeds only for the singlet.
  • J\={u}ro Ojima, Y\={o}ji Yokoyama, Michiko Enkaku
    1977 Volume 50 Issue 6 Pages 1522-1526
    Published: 1977
    Released: April 19, 2006
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    In order to examine the paratropic nature expected for a thirteen-membered ring system arising from polarization of the carbonyl group, the two benzannelated bisdehydro[13] annulenones, VI and IX, were prepared respectively by the aldol condensation of an appropriate aldehyde and an appropriate ketone followed by the oxidative coupling of the resulting acyclic ketone containing terminal acetylene groups. The NMR spectra indicate that both of VI and IX, as well as the respective protonated species, VII and X, are paratropic and paratropicities decrease in the sequence of VI>IX with the increasing number of fused benzene ring. The dibenzannelated annulenone (IX) and its precursor (VIII) were converted into the corresponding alcohols or ethers (XIIa, XIIb and XIa, XIb), respectively, to test the presence of the paratropic nature of IX. The NMR spectra of XIa, XIb and XIIa, XIIb, in addition to those of VIII and IX, suggested that IX seemed to be weakly paratropic. An attempt made to prepare the dibenzannelated bisdehydro[13]annulenyl anion (XIII) was unsuccessful.
  • Yoshihiro Shigemasa, Takashi Fujitani, Chikahiro Sakazawa, Teruo Matsu ...
    1977 Volume 50 Issue 6 Pages 1527-1531
    Published: 1977
    Released: April 19, 2006
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    By an analytical method using oxidation-reduction potential measurements of the formose reaction, which were previously shown to be useful for separately analyzing the induction and the formose-forming steps, the influence of various factors on each step and on the sugar yield were examined. It was found for the batchsystem formose reaction that the rate of both steps and the sugar yield are affected by the concentration of formaldehyde, the amount of calcium hydroxide, and also by the ratio of the two. The dissolved calcium ion is believed to be an essential catalyst for either the induction or the formose-forming step, with the hydroxy anion playing significant role as the catalyst for the latter step. The optimum conditions necessary for obtaining the sugars in high yields are discussed.
  • Tetsushi Yamashita, Hiroshi Yasueda, Yasushi Miyauchi, Nobuo Nakamura
    1977 Volume 50 Issue 6 Pages 1532-1534
    Published: 1977
    Released: April 19, 2006
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    The asymmetric addition of methanol to phenylmethylketene was carried out in the presence of propionylcinchonine and poly(acryloylcinchonine). The use of poly(acryloylcinchonine) produced additional products with higher optical yields than that of propionylcinchonine. The highest optical yield (35%) was obtained with the above polymeric catalyst at −78 °C. An insoluble, cross-linked polymer obtained by the co-polymerization of acryloylcinchonine with N,N′-diacryloylhexamethylenediamine, was also used as a catalyst. The products obtained for the cross-linked polymer showed a linear correlation between logkR/ks and 1/T while those with non-cross-linked poly(acryloylcinchonine) exhibited a relationship deviating somewhat from linearity. A linear relationship was also observed using insoluble, cross-linked poly(acryloylquinine).
  • Atsuyoshi Ohno, Takahide Kimura, Hiroyuki Yamamoto, Seung Geon Kim, Sh ...
    1977 Volume 50 Issue 6 Pages 1535-1538
    Published: 1977
    Released: April 19, 2006
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    The driving force for the catalytic activity of metal ions on the reduction of α-keto esters with an NAD(P)H-model compound has been discussed. The scope of the reaction and spectroscopic investigations as well as molecular orbital consideration have revealed that the transition state of the reaction consists of a ternary complex in analogy with a coenzyme–enzye–substrate complex in an enzymic system. It is concluded that, at the transition state, one electron migrates from a model compound to a substrate through a metal ion, which is followed by the transfer of a proton.
  • Yoshiaki Watanabe, Masato Okada, Yusuke Izumi, Yukio Mizutani
    1977 Volume 50 Issue 6 Pages 1539-1544
    Published: 1977
    Released: April 19, 2006
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    The kinetics of the direct catalytic conversion of acetone and hydrogen into methyl isobutyl ketone (MIBK) were investigated in the liquid phase using palladium–zirconium phosphate as a catalyst. Kinetic studies on the conversion of acetone into mesityl oxide (4-methyl-3-pentene-2-one) and its hydrogenation were separately carried out using the same catalyst. It was found that the direct reaction proceeded via a sequence of processes: mesityl oxide was first formed by condensation of acetone on acid sites of the catalyst and MIBK was then produced by hydrogenation of the mesityl oxide on palladium metal in the catalyst. Moreover, the experimental results were well interpreted by assuming that the condensation of acetone was controlled by a surface reaction between the acetone molecules adsorbed on the catalyst surface and that the rate of hydrogenation of mesityl oxide was determined by a surface reaction between dissociated hydrogen atoms and adsorbed mesityl oxide molecules.
  • Daiyo Terunuma, Satoshi Hatta, Tsunao Araki, Tadashi Ueki, Tsutomu Oka ...
    1977 Volume 50 Issue 6 Pages 1545-1548
    Published: 1977
    Released: April 19, 2006
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    The in situ reaction of dialkoxydichlorosilanes, such as dimethoxy-, diethoxy-, dipropoxy-, dibutoxy-, and diisobutoxydichlorosilane, with isoprene and magnesium in tetrahydrofuran (THF) was investigated. It was found that the double annelation product, i.e., 2,7-dimethyl-5-silaspiro[4.4]nona-2,7-diene (1), was obtained from diethoxy-, dipropoxy-, and dibutoxydichlorosilane in 87.0, 65.2, and 66.5% yields respectively. On the other hand, the reaction of dimethoxy- and diethoxydichlorosilane with butadiene and magnesium in THF gave 5-silaspiro[4.4]nona-2,7-diene (7) in 20.7 and 35.4% yields respectively. Several silaspirononane derivatives were synthesized from 1.
  • Osamu Itoh, Tsutomu Okita, Makoto Umezu, Masashi Inoue, Katsuhiko Ichi ...
    1977 Volume 50 Issue 6 Pages 1549-1551
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    Lithium aluminium hydride reduction of 6,6-dimethylspiro[2.5]octane-4,8-dione in tetrahydrofuran gave cis- and trans-6,6-dimethylspiro[2.5]octane-4,8-diols. Almost the same ratio of cis: trans=1:2 was obtained with various substrate-reagent ratios. In the case of Meerwein-Ponndorf-Verly reduction, however, cis-diol was obtained almost exclusively. It is clear that the former reduction gave kinetically-controlled products and that the latter gave thermodynamically-stable products. Unusual results were obtained by changing the hydrolysis conditions for the lithium aluminium hydride reduction products and these are explained assuming that the intermediate aluminium alkoxide is oxidized by acid.
  • Kazuo Tachibana, Motoo Tori, Yoshihiko Moriyama, Takahiko Tsuyuki, Tak ...
    1977 Volume 50 Issue 6 Pages 1552-1557
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    3β,4β-Epoxyshionane (15) was treated with boron trifluoride etherate in ether at −30 °C to give dihydrobaccharis oxide (4; yield 17%), 4α-fluoroshionan-3β-ol (17; 10%), D: B-friedo-bacchar-5-en-3β-ol (18; 18%), D:B-friedo-bacchar-5(10)-en-3β-ol (20; 15%), and D: C-friedo-bacchar-7-en-3β-ol (21; 15%). The reaction in benzene, toluene, cyclohexane, or in hexane at −5 °C or at room temperature yielded bacchar-12-en-3β-ol (5), D: C-friedo-bacchar-8-en-3β-ol (25), 18, 20, and 21. The reaction product ratios in the same reaction in various solvents are listed in Table 1.
  • Takumi Oshima, Toshikazu Nagai
    1977 Volume 50 Issue 6 Pages 1558-1561
    Published: 1977
    Released: April 19, 2006
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    It was found that a number of diazoalkanes (I) bearing a relatively small substituent reacted with o-sulfobenzoic anhydride (II) in acetonitrile at an ordinary temperature to give the o-(substituted glycoloyl)benzenesulfonic acid sultones (IV), which correspond formally to the products from the insertion into the C–O bond of II by the carbenes, while diaryldiazomethanes underwent decomposition under the same conditions to produce the corresponding tetraarylethylenes (V) instead of the inserted products (IV). The olefin formation reaction was very fast compared to the sultone formation and was considered to be the result of the acid-catalyzed decomposition caused by the contaminant o-sulfobenzoic acid (III) which was derived from II. The kinetics and the mechanism of these reactions were discussed on the basis of the nature of diazoalkanes.
  • Masako Sakuragi, Hirochika Sakuragi, Masaki Hasegawa
    1977 Volume 50 Issue 6 Pages 1562-1566
    Published: 1977
    Released: April 19, 2006
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    Irradiation of 1,2-diphenylcyclobutene (1) in methanol affords the methyl ethers, 1,2-diphenyl-1-methoxycyclobutane (2a) and 1-(α-methoxybenzyl)-1-phenylcyclopropane (3a). In acetic acid and in a mixture of water and dioxane, the corresponding esters (2b and 3b) and alcohols (2c and 3c) are formed, respectively. Evidence supporting the involvement of a singlet species was obtained upon finding that the fluorescence of 1 is substantially quenched upon the addition of methanol or acetic acid to a solution of 1 in hexane.
  • Kenji Tsujihara, Hironori Kurita, Mitsutaka Kawazu
    1977 Volume 50 Issue 6 Pages 1567-1571
    Published: 1977
    Released: April 19, 2006
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    Mesitylenesulfonyl chloride reacted selectively with primary hydroxyl groups of cycloheptaamylose to give hexakis (6-O-mesitylsulfonyl)cycloheptaamylose (II) and heptakis(mesitylsulfonyl)cycloheptaamylose (I). The selectivity of mesitylenesulfonyl chloride in the preferential sulfonylation is 24 times larger than that of tosyl chloride. Pure hexakis(6-azido-6-deoxy)cycloheptaamylose (III) and hexakis(6-amino-6-deoxy)cycloheptaamylose (IV) were synthesized from II. Pure heptakis(6-amino-6-deoxy)cycloheptaamylose (VII) and mixture of positional isomers of hexakis(6-amino-6-deoxy)mesitylsulfonylcycloheptaamylose (VIII)* were obtained by the catalytic hydrogenation of the corresponding azido compounds V and VI,* which were themselves given by the reaction of I with sodium azide. These amino derivatives, IV, VII, and VIII,* showed significant antimicrobial activities against such gram-negative bacteria as Escherichia, Shigella, and Pseudomonas. These compounds also exhibited hypocholesterolemic effects in the chick when added in the diet for two weeks, probably through sequestration of intestinal bile acids.
  • Kin-ichi Tadano, Yasufumi Emori, Mitsukuni Ayabe, Tetsuo Suami
    1977 Volume 50 Issue 6 Pages 1572-1574
    Published: 1977
    Released: April 19, 2006
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    Three 9-(3-amino-2,4,5-trihydroxycyclopentyl)adenines and their N-acyl derivatives were prepared as carbocyclic analogs of 3′-amino and 3′-acetamido-3′-deoxyadenosine from the three diastereomers of diaminocyclopentanetriol and 4-amino-6-chloro-5-nitropyrimidine.
  • Takashi Matsumoto, Shuji Usui, Toshitaka Morimoto
    1977 Volume 50 Issue 6 Pages 1575-1579
    Published: 1977
    Released: April 19, 2006
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    The condensation of β-cyclocitral (4); with 3-isopropyl-4-methoxybenzyl chloride (5) in the presence of lithium naphthalenide gave an alcohol (6), which was then oxidized to the corresponding α,β-unsaturated ketone (7). The Intramolecular cyclization of 7 with polyphosphoric acid yielded (±)-12-methoxyabieta-8,11,13-trien-6-one (8) and its cis-isomer (9), which was then successfully converted into 8 via an enol acetate (11). The 8 ketone was dem ethylated with boron tribromide to give a phenol (18), and this was then reduced with lithium aluminium hydride to yield the corresponding alcohol (19). The oxidation of the C-11 position in 19 with benzoyl peroxide gave (±)-12-benzoyloxyabieta-8,11,13-trien-6β,11-diol (20), which, on reduction with lithium aluminium hydride and subsequent oxidation with Jones reagent, afforded (±)-taxodione (1). The reductive cleavage of the hydroxyl group in 6 with dichloroaluminium hydride, followed by cyclization, gave (±)-ferruginyl methyl ether (12), which was then demethylated with boron tribromide to produce (±)-ferruginol (2). Further, the oxidation of 12 with chromium trioxide, followed by demethylation, gave (±)-sugiol (3).
  • Tomo Nishimura, Tsutomu Tsuchiya, Sumio Umezawa, Hamao Umezawa
    1977 Volume 50 Issue 6 Pages 1580-1583
    Published: 1977
    Released: April 19, 2006
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    3′,4′-Dideoxykanamycin B was prepared from kanamycin B via 4″,6″-O-cyclohexylidenation, N-benzyloxycarbonylation, 3′,4′,2″-tri-O-benzylsulfonylation, double bond formation at C-3′,4′, removal of the cyclohexylidene group, simultaneous removal of the N,O-protecting groups with sodium metal in liquid ammonia and hydrogenation of the resulting 3′,4′-dideoxy-3′-eno-kanamycin B.
  • J\={u}ro Ojima, Miyako Ishiyama, Akihiko Kimura
    1977 Volume 50 Issue 6 Pages 1584-1587
    Published: 1977
    Released: April 19, 2006
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    The benzannelated annulenones VII and XI have been synthesized to establish the effect of annelation of benzene ring on the seventeen-membered ring system. An examination of the NMR spectra suggested that both of VII and XI are paratropic and the paratropicities decrease in the order of VII>XI with the number of benzene ring fused to seventeen-membered ring system.
  • Hiroaki Taguchi, Hisashi Yamamoto, Hitosi Nozaki
    1977 Volume 50 Issue 6 Pages 1588-1591
    Published: 1977
    Released: April 19, 2006
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    The title adducts are produced upon treatment of a mixture of polyhalomethane and a carbonyl compound with a hindered lithium amide. The kinetically controlled, selective lithiation of the halide enables us to avoid a troublesome procedure involving preformed lithium carbenoid. The halide components examined are dichloromethane, dibromomethane, diiodomethane, chloroform, and bromoform, while the carbonyl ones are ubiquitous ketones and nonanal. A gem-dichloroallyllithium is generated similarly from 3,3-dichloropropene and, furthermore, the procedure is successfully extended to the Darzens-type reaction of α-halo esters.
  • Hiroaki Taguchi, Hisashi Yamamoto, Hitosi Nozaki
    1977 Volume 50 Issue 6 Pages 1592-1595
    Published: 1977
    Released: April 19, 2006
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    A general method of transforming a cyclic ketone to the next higher ring homolog chlorinated at the α-carbon or alternatively to its parent ketone is described. Treatment of a dichloromethyllithium-carbonyl adduct 2 with butyllithium affords a β-oxido carbenoid 3 at low temperature. Upon warming, 3 decomposes to a lithium enolate 4, which is quenched with diluted hydrochloric acid to give the α-chloro ketone 5. Cycloalkanone is converted to a one-carbon ring enlarged halogenated ketone. Meanwhile, dibromomethylcarbinol 7 is transformed to the halogen-free ketone 8 via monobromo β-oxido carbenoid upon treatment with butyllithium. α-Methyl substituted ketone is exclusively converted to the β-methyl substituted homolog and therefore dl-muscone is synthesized from cyclotetradecanone according to this new method.
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