Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 58 , Issue 3
Showing 1-50 articles out of 65 articles from the selected issue
  • Hitoshi Saima, Kaoru Fujimoto, Hiro-o Tominaga
    1985 Volume 58 Issue 3 Pages 795-802
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Synthesis gas reactions over hybrid catalysts composed of Pd/SiO2 and zeolites and methanol conversion on the same zeolites were studied. The selectivities to aromatic hydrocarbons were about 30% for the methanol conversions over ZSM-5, de-aluminated mordenite, and de-aluminated Y type zeolite (DAY), which possess strong acid sites. When ZSM-5 or mordenites were combined with Pd/SiO2 and subjected to synthesis gas conversion, the selectivities to aromatic hydrocarbons were between 10% and 30%. However, the synthesis gas reaction over the hybrid catalyst composed of Pd/SiO2 and DAY, gave few aromatic hydrocarbons, but aliphatic paraffins with 2 to 6 carbon atoms. Over large pore zeolites like DAY, the diffusion of olefins is so quick that most of the olefins come out of pores to be hydrogenated to paraffins on the Pd/SiO2 catalyst. In contrast, because of the slow diffusion of olefins in the medium size pores of ZSM-5 or mordenite, olefins stay in the pores for long enough to form aromatic hydrocarbons on the strong acid sites before being hydrogenated.
  • Akio Furusaki, Shin-ichiro Katsuragi, Katsunao Suehiro, Takeshi Matsum ...
    1985 Volume 58 Issue 3 Pages 803-809
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The molecular structures of isolaurallene and neolaurallene, diastereomeric nonterpenoids (C15H20O2Br2) from the red algae Laurencia, have been determined by X-ray crystallographic analysis. The crystal data are as follows: isolaurallene, orthorhombic, space group P212121, a=10.393(2), b=27.824(4), c=5.397(1) Å, Z=4, Dc=1.669 g cm−3; neolaurallene, monoclinic, space group P21, a=13.338(7), b=4.929(1), c=12.435(5) Å, β=98.22(4)°, Z=2, Dc=1.609 g cm−3. The structures were solved by the heavy-atom method, and refined by the block-diagonal least-squares method; the final R-values were 0.076 and 0.069 respectively. The (Z)-2,3,4,7,8,9-hexahydrooxonin rings in the two substances possess essentially the same conformation. The MM2 force–field calculations have shown that this conformation is almost identical to the most stable one of the 11 minimum-energy conformations found for (Z)-2,3,4,7,8,9-hexahydrooxonin. For comparison, the conformations of (Z)-cyclononene have also been examined by the force–field calculations. Of its 10 minimum-energy conformations obtained, the asymmetric one which Favini et al. already studied has the lowest energy.
  • Yoshimi Sueishi, Kazuo Ohtani, Norio Nishimura
    1985 Volume 58 Issue 3 Pages 810-814
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The kinetics of the thermal cis-to-trans isomerization of N,N′-diacylindigos(DAI) in various solvents and under high pressures has been studied. N,N′-Dibenzoylindigos(DBI) isomerize about 10 times slower than molecules not having a benzene ring in the acyl groups. The values of the activation volumes were about 8.0 cm3 mol−1 for the former and about 3.0 cm3 mol−1 for the latter. It was suggested that the thermal isomerization proceeds via the biradical mechanism. The positive values of the activation volume have been interpreted in terms of the increase in the intrinsic volume upon activation. The differences in the isomerization rates and the activation parameters between DBI and the others have been ascribed to an additional interaction between the two phenyl rings in the acyl groups in the cis-ground state.
  • Yoshikazu Fujita, Itsuo Mori, Shoko Kitano, Hiroshi Kawabe, Yozo Koshi ...
    1985 Volume 58 Issue 3 Pages 815-820
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    On this basis of the coloration formed with o-hydroxyhydroquinonephthalein, an anionic dye, and iron(III) in aqueous media, trace amounts of phosphorus(as orthophosphate ion) was determined. A sample solution containing posphorus and the reagent blank in an amber-colored test tube with a stopper were heated at 40 °C for 20 min in the presence of poly(oxyethylene)sorbitan monolaurate, a nonionic surfactant, as a dispersion agent. Beer’s law was obeyed over the range of ≈1 μg/10 cm3 of phosphorus, and the apparent molar absorptivity of the complex was 2.5×105 dm3 mol−1 cm−1 at 610 nm. The present method was applied to the determination of total phosphorus in water — a sample solution containing small amounts of metal ions —, and the recovery percentage was satisfactory, about 95%. Other compounds containing phosphorus such as 5′-adenosine triphosphate could also be determined without a preliminary treatment.
  • Kazuo Kojima, Jiro Matsuda
    1985 Volume 58 Issue 3 Pages 821-825
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The absorption spectra of Co(III) and Co(II) in the single crystals of the Keggin-structure compounds, K5[CoIIIW12O40nH2O and K6[CoIIW12O40mH2O, have been measured at 77 K. The spectra of these complexes in aqueous solutions have also been observed. All the spectra have been interpreted using crystal-field theory by assuming that a Co(III) or Co(II) ion is in Td symmetry. The parameters, Dq, B, and CB can be evaluated as 780 cm−1, 630 cm−1, and 4.7 respectively for the Co(III) complex, and 460 cm−1, 650 cm−1, and 4.5 respectively for the Co(II) complex.
  • Toshio Ishii, Shigeru Ohba, Masatoki Ito, Sachio Fukushi, Yoshihiko Sa ...
    1985 Volume 58 Issue 3 Pages 826-832
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Crystal structures of the two isomeric Co(III) complexes with sexidentate ligands, (NH2CH2CH2)2NC*H(CH3)CH2C*H(CH3)N(CH2CH2NH2)2 (hereafter abbreviated as R,R- and R,S-tptn) and of the Co(III) complex with a sexidentate ligand, (NH2CH2CH2)2NCH2CH2CH2N(CH2CH2NH2)2 (abbreviated as ttn) were determined by an X-ray diffraction method. The crystal data and the final R factors are: (1) [Co(R,R-tptn)](ClO4)3·H2O, tetragonal, P42212, a=12.800(1), c=15.312(1) Å, V=2509(1) Å3, Z=4, R=0.053 for 1627 observed unique reflections, (2) [Co(R,S-tptn)]Cl3·3H2O, monoclinic, P21a, a=16.778(6), b=14.296(2), c=9.478(4) Å, β=110.99(3)°, V=2123(1) Å3, Z=4, R=0.045 for 3583 reflections and (3) [Co(ttn)]Br3·H2O, trigonal, P\={3}cl, a=14.436(4), c=15.718(9) Å, V=2837(2) Å3, Z=6, R=0.096 for 1183 reflections. The equatorial preference of the methyl groups in the central six-membered chelate ring formed by Co and 2,4-pentanediamine moiety of R,R- and R,S-tptn has been recognized. In (1) the six-membered chelate ring adopts a twist boat form as in (3) with the two C–CH3 bonds in equatorial positions. In (2) the six-membered chelate ring takes a largely flattened chair form with the two C–CH3 bonds again in equatorial positions. The effect of an elongation of the Co–N bond distance on the energy of the first absorption band was discussed.
  • Junko Akashi, Tomoko Kojima, Yoshio Uchida, Hirotoshi Sano
    1985 Volume 58 Issue 3 Pages 833-837
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The G-values for the reduction of iron(III) to iron(II) state caused by 6Li(n,α)T reaction in Li3[Fe(C2O4)3]·4.5H2O and in anhydrated Li3[Fe(C2O4)3] were determined by taking into account the saturation of the effect of increasing neutron fluence. The contribution of the fast neutrons and γ-rays in a nuclear reactor to the reduction was estimated by using a cadmium tube, and by using the results estimated in the 60Co γ-ray irradiation, respectively. The G(Fe3+→Fe2+)-value in the radiolysis caused by 6Li(n,α)T reacation in Li3[Fe(C2O4)3]·4.5H2O is larger than that in the γ-ray radiolysis, and is also larger than the G-value for anhydrated Li3[Fe(C2O4)3], suggesting that the radiolysis of the water of crystallization contributes to the reduction of the iron(III) species.
  • Kazuaki Sukata
    1985 Volume 58 Issue 3 Pages 838-843
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The effects of alumina impregnated with KOH (KOH/Al2O3) and a mixture of alumina and powdered KOH (KOH+Al2O3) have been examined using the alkylation of benzamide under various conditions. In each case, alkylation occurs exclusively in the pores of the alumina, the extent depending upon the alumina-pore size. For both yield and selectivity for N-monoalkylation, KOH+Al2O3 is superior to KOH/Al2O3. Dioxane is the best of the solvents employed. It is proposed that, in dioxane, an enolate-like species, (Remark: Graphics omitted.), exists as stable ion-pair aggregates, which are the true reactants in the pore. This method, using KOH/Al2O3 or KOH+Al2O3, has been applied to N-alkylation of the other amides, giving the N-monoalkylated products in substantial yields with extremely high selectivities. 2-Phenylacetamide is regioselectively N-monoalkylated in high yields. This regioselectivity is explained in terms of steric hindrance.
  • Seijiro Matsubara, Takashi Okazoe, Koichiro Oshima, Kazuhiko Takai, Hi ...
    1985 Volume 58 Issue 3 Pages 844-849
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Isomerization of primary allylic alcohols proceeds in dichloromethane at 25 °C in the presence of the catalyst prepared in situ from VO(acac)2 or MoO2(acac)2, and Me3SiOOSiMe3 to give tertiary isomers in good yields. The catalysts are also effective for the rearrangements of sec.tert. allylic alcohols. The isomerization of an allenyl allylic alcohol, 6-methyl-1,2,5-heptatrien-4-ol, gives either (E)-2-methyl-3,5,6-heptatrien-2-ol or (E)-6-methyl-3,5-heptadien-2-one selectively depending on the reaction conditions.
  • Mitsuo Sekine, Shin-ichi Nishiyama, Takashi Kamimura, Yumi Osaki, Tsuj ...
    1985 Volume 58 Issue 3 Pages 850-860
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The fully-protected pAUG (15) and pAUGACC (21) were synthesized by the phosphotriester approach where the phenylthio group was employed as the internal and 5′-terminal phosphate-protecting groups. The partially unblocked oligomers (32) and (33), obtained by alkaline treatment of (15) and (21), were condensed with a capping reagent (1a) in the presence of imidazole by activation with silver nitrate to afford the capped trimer and hexamer protected with the acid-labile protecting groups, i.e., 4,4,′4″-trimethoxytrityl (TMTr), 4-monomethoxytrityl (MMTr), tetrahydropyran-2-yl (THP), and methoxymethylene (mM) groups. The protected capped oligomers were unblocked by a dilute HCl solution to afford m7G5′ pppAUG and m7G5′ pppAUGACC, which were purified by HPLC and characterized by enzyme assays.
  • Tadao Uyehara, Jun-ichi Yamada, Tadahiro Kato, Ferdinand Bohlmann
    1985 Volume 58 Issue 3 Pages 861-867
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The exo-7-(4-methyl-3-pentenyl) derivative of 3-carene (1a), the original structure reported for (±)-isosesquicarene, was synthesized starting from tropone, and it was found that 1a is not identical with natural isosesquicarene. The structure of isosesquicarene was reinterpreted as endo-7-(4-methyl-3-pentenyl) derivative of 3-carene (1b). The first total synthesis of (±)-isosesquicarene, 1b, has been accomplished on the basis of the photochemical transformation of 4-methylbicyclo[3.2.2]nona-3,6-dien-2-one into the 7-exo-methylbicyclo[4.1.0]hept-2-ene.
  • Tetsuo Katsuyama, Junichi Shida
    1985 Volume 58 Issue 3 Pages 868-873
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Digital first-order derivative spectrophotometry was applied to the determination of iron with 1,10-phenanthroline. Under the recommended conditions, a linear relationship was confirmed between the first-derivative value and the iron concentration. The present method gives accurate results for iron, ranging from 1.6×10−7 to 8×10−5 mol dm−3 (8.9 μg dm−3–4.5 mg dm−3). The relative standard deviations for the determination of 4.8×10−5, 4.8×10−6, and 4.8×10−7mol dm−3 of iron(III) were 0.37, 0.38, and 0.93%, respectively. The effects of 63 diverse ions were examined. The present method was applied to the determination of iron in practical samples, i.e., river water, waste water and sea water.
  • Mitsunobu Sato, Masao Kosaka, Masatoshi Watabe
    1985 Volume 58 Issue 3 Pages 874-880
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The (L-alanine-N-acetato)(L-histidinato)chromium(III) monohydrate complex, C11H14N4O6Cr, has been synthesized and its crystal structure has been determined from three dimensional X-ray-diffractometer data. The crystals are orthorhombic, of the space group P212121, with 4 molecules in a cell with these dimensions: a=11.052(1), b=13.959(3), and c=9.616(2) Å. Block-diagonal least-squares refinements using 1318 independent nonzero reflections have yielded a conventional R factor of 0.033. The structure consists of monomeric [Cr(L-alama)(L-his)] units and water molecules. The L-alama ligand coordinates to the metal as of dianion, with Cr–O(acetyl), Cr–N, and Cr–O(alanine) bond lengths of 1.960(3), 2.078(5), and 1.946(4) Å respectively. The histidinate monoanion coordinates through Cr–N(amino), Cr–N(imidazole), and Cr–O bonds 2.062(4), 2.036(5), and 1.957(4) Å long respectively. The geometry at chromium is a distorted octahedron, with cis bond angles in the range from 80.1(2) to 99.3(2)°. Among the six possible isomers of the [Cr(L-alama)(L-his)] complex, only one isomer was prepared and crystallized; its geometry was R-L-trans(O)cis(N).
  • Yoshinari Baba, Yutaka Ikeda, Katsutoshi Inoue
    1985 Volume 58 Issue 3 Pages 881-884
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Solvent extraction of mercury(II) from hydrochloric acid with 1,2-bis(hexylthio)ethane (=BHTE=\barS) in 1,2-dichloroethane has been studied at 30 °C. Mercury(II) was found to be extracted into pure 1,2-dichloroethane without extractants, which is due to the physical partition of the neutral species, HgCl2. The partition coefficient, KD, was evaluated as KD=0.314. It was clarified that the extraction mechanism with BHTE can be explained in terms of solvation by BHTE and that 1:1 metal: the ligand complex is formed in the organic phase as follows.
    \barS+HgCl2\ ightleftharpoons‾HgCl2·S  Ke
    The extraction equilibrium constant, Ke, was evaluated as Ke=1.61×103 dm3 mol−1.
  • Gin-ya Adachi, Hiroki Sakaguchi, Ken-ichi Niki, Hiroshi Nagai, Jiro Sh ...
    1985 Volume 58 Issue 3 Pages 885-889
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Thin films of LaNi5 have been prepared by means of a flash evaporation-deposition technique. Electric resistivity measurements on these films were carried out in an atmosphere of hydrogen. The films formed on quartz substrates were amorphous. Resistivities initially increased and then decreased during the absorption of hydrogen. During the desorption process, the reverse phenomenon was observed. The effect of the thickness of the films on the electric properties, during the hydrogen absorption-desorption process, was also studied. Sample pulverization could be avoidable by using films of less than 10 μm in thickness. The hydrogen contents of the films were determined by the quartz-crystal mass-monitoring (QCMM) method.
  • Shang Xian, Kazuhiko Seki, Hiroo Inokuchi, Shimpei Hashimoto, Nobuo Ue ...
    1985 Volume 58 Issue 3 Pages 890-899
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    UV photoelectron spectra were measured for polypropylene (PP), poly(vinyl fluoride) (PVF), 1,2-polybutadiene (1,2-PBD), poly(vinyl chloride) (PVC), and poly(vinyl alcohol) (PVA). Their threshold ionization energies were found to be 8.5, 9.2, 7.5, 8.8, and 8.0 eV (1 eV≅0.1602 aJ), respectively. The evolution of their electronic structures (from those of small related molecules) were analyzed, mainly, by using the photoelectron spectra of these small compounds (including the new data of 1,2-propanediol). The data of previously measured polyethylene (PE) and polystyrene (PS) were analyzed together. With the results, the polymers were classified into three groups according to the increasing order of localization of the positive hole in the cationic state: (1) PE, PP, and PVF, (2) 1,2-PBD, PVC, and PVA, and (3) PS as a representative of aromatic-pendant polymers.
  • Isao Mochida, Kiyoshi Yata, Hiroshi Fujitsu, Yoshinobu Komatsubara
    1985 Volume 58 Issue 3 Pages 900-904
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The catalytic activity of a copper(II) salt of polymolybdophosphoric acid (Cu1.1H0.8PA) for the reduction of NO with the supporting active carbon into N2 and N2O was studied at 400 °C using a fixed bed flow reactor. A considerable activity was observable at a stationary state where the spill-over of oxygen left on the active site of the acid to the carbon surface appeared to be rate-determining. The activity of the salt was much higher than for component oxides produced through its decomposition at higher temperatures. This suggested that the active site was characteristic to the salt (very probably the reduced site in the salt). The reaction mechanism in terms of the reaction paths, the N2O/N2 selectivity, and the roles of the supporting active carbon are discussed based on kinetic investigations.
  • Michio Kimura
    1985 Volume 58 Issue 3 Pages 905-910
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The title compound has been synthesized by the novel condensation reaction of p-chlorophenol with oxalic and sulfuric acids; its crystal and molecular structures have been determined by the single crystal X-ray diffraction method. The space group is C2/c. There are eight molecules of the title compound in the unit cell of dimensions a=21.316(9), b=17.267(4), c=9.158(6) Å, and β=94.05(5)°. The structure was solved by the direct method and refined by the block-diagonal least-squares method to a value of 0.088 for R using 1993 independent observed reflections with Fo>3σ(Fo). The molecule possesses three phenyl rings fused to spirolactone and the dihedral angles between the phenyl rings are 73.60°, 83.60°, and 22.81°.
  • Hiroshi Matsui, Takeo Hisano, Toshio Terazawa
    1985 Volume 58 Issue 3 Pages 911-915
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The kind of carbon-containing adsorbate formed on a platinum electrode from methanol in an acid medium was identified by an electrochemical method. Certain improvements were made in view of the harmful effects of the following factors on the QF value, the quantity of electricity required to form adsorbate. The factors: a) The amounts of dissolved oxygen in both solution and electrode itself; b) the concurrent oxidation of the adsorbate in the adsorption process; and c) the presence of by-products of the methanol oxidation, formaldehyde and formic acid. By appropriate procedures, these effects could be minimized or corrected. The ratio QFQox, where Qox was an electric quantity required to oxidize completely that amount of adsorbate corresponding to the QF, was found to be 1.8–2.0 when the potential was 0.30–0.54 V, and the methanol concentration 0.005–1 mol dm−3. It was thus concluded that the adsorbate was almost exclusively COad.
  • Yoshinori Nagase, Tuo Jin, Hideshi Hattori, Tsutomu Yamaguchi, Kozo Ta ...
    1985 Volume 58 Issue 3 Pages 916-918
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Five kinds of iron oxide catalysts promoted with sulfur were prepared by impregnating Fe(OH)3 with (NH4)2SO4 and by treating Fe2O3 and Fe(OH)3 with H2S and SO2. Changes in acidic properties of the catalysts with changes in oxidation states of sulfur were investigated by test reactions such as isomerization of cyclopropane and dehydration of 2-propanol over the oxidized or reduced catalysts. It has been found that the generation of acidic properties of the catalysts was independent of the kinds of the starting sulfur compounds, but dependent on the oxidation states of the sulfur. The sulfur in the highest oxidation state was responsible for the strongly acidic property of the catalyst.
  • Takahiro Wada, Hiroshi Yoneno
    1985 Volume 58 Issue 3 Pages 919-925
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Influences of preheating temperature were studied on crystallization of CH3CO2Na·3H2O from its melts containing a small amount of Na4P2O7 or Na2HPO4 as a crystal nucleation catalyst. The relation between the activation process of these nucleation catalysts and their deactivation temperatures was investigated in detail. Aging of nucleation catalyst which was preceded by forced crystallization of CH3CO2Na·3H2O from its melt containing the catalyst, largely affects the catalyst’s deactivation temperature. Whenever Na4P2O7 or Na2HPO4 was used as a nucleation catalyst, the deactivation temperature was raised by lengthening aging time at a constant aging temperature. When the catalysts were aged for 4 d at 20 °C, the aging effect on them was almost saturated. At lower temperatures, longer aging times were required for saturation of the effect. The results obtained are discussed with a modified adsorption model, which takes into account commensurate-incommensurate phase transition of solid adsorbate.
  • Hiroshi Sakai, Manabu Mizota, Yutaka Maeda, Takakazu Yamamoto, Akio Ya ...
    1985 Volume 58 Issue 3 Pages 926-931
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Resonance Raman and 129I Mössbauer spectroscopy have been used in a study of iodine doped poly(thienylene)s, which are chemically synthesized by the polymerization of dibromothiophenes. It is shown that the iodine species in the polymers are present predominantly in the form of a polyiodide which consists of unsymmetrical I3 and I2 units. That is, the iodine molecule doped is reduced by taking electrons from the polymer in a similar manner to iodine doped in polyacetylene. This result is consistent with the fact that poly(thienylene)s undergo an increase in electrical conductivity upon doping with iodine.
  • Shin-ichi Ishiguro, Hideo Wada, Hitoshi Ohtaki
    1985 Volume 58 Issue 3 Pages 932-937
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Solvation and protonation of 1,10-phenanthroline (phen) have been studied by potentiometry and calorimetry in various aqueous dioxane solutions. Protonation reactions were studied in the mixtures (the dioxane content x=0–0.4 mole fraction) containing 0.3 mol dm−3 NaCl as a constant ionic medium at 25 °C. Potentiometric and calorimetric titration curves obtained in the range of −log[H+]=2–7 were well explained in terms of the formation of Hphen+ and H(phen)2+, and the formation constants, enthalpies and entropies of formation of the species were determined. The formation constants of the both species gradually decreased with increasing x, and then the formation of H(phen)2+ became negligibly small at x>0.1, while the enthalpy and entropy of formation of Hphen+ first decreased and then increased with increasing x and thus minima were found at x=0.05. Enthalpies of solution of anhydrous 1,10-phenanthroline were also determined in both neutral (x=0–1) and acidic (0.1 mol dm−3 HCl, x=0–0.4) aqueous dioxane solutions. By knowing enthalpies of solution of 1,10-phenanthroline in acidic solutions and of formation of Hphen+ in the mixed solvents, enthalpies of solution of 1,10-phenanthroline in neutral solutions (ΔH°s(phen)) were evaluated and compared with those directly obtained in the neutral solutions (ΔH°s,neutral). A significant difference was found between ΔH°s(phen) and ΔH°s,neutral in the range x<0.3, which could be ascribed to the formation of stacked species of 1,10-phenanthroline molecules, (phen)n. The variation of ΔH°s(phen) with x was explained in terms of the enhanced solvation of dioxane to phenanthroline molecules owing to breaking of the hydrophobic water structure around them. Solvent effects on the formation of Hphen+ and H(phen)2+ were discussed in terms of different solvation behavior of 1,10-phenanthroline and proton with x.
  • Woo-Sik Jung, Hiroshi Tomiyasu, Hiroshi Fukutomi
    1985 Volume 58 Issue 3 Pages 938-942
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    17O NMR chemical shifts, UV-visible and IR spectra of a series of [UO2Ln](ClO4)2 (L=unidentate oxygen-donor ligand; n=coordination number) complexes in nonaqueous solvents have been measured. The electronic transition bands of the UO22+ entity shift toward lower energies with the increase in base strength of ligands in the equatorial plane. The asymmetric stretching frequencies of U=O bands are also affected by the base strength of equatorial ligands and correlated with the lowest electronic transition energies of uranyl complexes with the same geometry. The 17O chemical shifts are shown to be related to the lowest electronic transition energies of uranyl complexes. It appears that oxygen isotope shifts in 17O NMR spectra of the uranyl ion are predominantly attributed to the increase in the lowest electronic transition energies.
  • Kan Kanamori, Ikuko Bansho, Kiyoyasu Kawai, Keiji Akamatsu, Yoichi Shi ...
    1985 Volume 58 Issue 3 Pages 943-947
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Three geometrical isomers of [Co(NO2)2(NH3)2(en)]+ were newly prepared. Two cis(NO2) isomers (trans(NH3) and cis,cis) were clearly differentiated on the basis of the polarizabilities of the Raman bands due to Co–N(NH3 and en) stretching vibrations. The Raman polarization measurement was also applied successfully to the determination of the geometrical configurations of two [Co(CN)2(NH3)2(en)]+ isomers. The structural assignments were substantiated by optical resolution of the cis,cis isomers of [Coa2(NH3)2(en)]+ (a=NO2 and CN).
  • Kenzo Kitayama, Takashi Katsura
    1985 Volume 58 Issue 3 Pages 948-956
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The phase equilibria in the systems, Pr2O3–V2O3–V2O5, Tb2O3–V2O3–V2O5, and Y2O3–V2O3–V2O5, were established at 1200 °C by changing the oxygen partial pressure from −1.20 (in the CO2) to 7.50 in −log (PO2/Pa) for Pr2O3 and Tb2O3 systems, and from −4.32 (in the air) to 7.50 in −log (PO2/Pa) for Y2O3 system. In the first system 0.81Pr2O3·0.19V2O5(A) and 3Pr2O3·V2O5(B), in the second 0.81Tb2O3·0.19V2O5(A′), and in the last one 4Y2O3·V2O5(A″) were stable in addition to Ln2O3, LnVO4, LnVO3, VnO2n−1 (n=2–7, and Ln means Pr, Tb, and Y), and VO2 under the present experimental conditions. On the basis of the established phase diagrams, the standard Gibbs energies (ΔG°) of reactions appeared in the systems were calculated. Compounds A, B, PrVO3, A′, A″, and LnVO4 have nonstoichiometric compositions. ΔG° values for the reactions and crystallographic values of the compounds were represented as a function of the ionic radius of lanthanoid (including Y) elements.
  • Hideaki Monjushiro, Katsuo Murata, Shigero Ikeda
    1985 Volume 58 Issue 3 Pages 957-961
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Chemical interactions between aromatic nitro compounds and thin aluminium oxide grown on aluminium film were studied by the combined use of inelastic electron tunneling spectroscopy (IETS) and X-ray photoelectron spectroscopy (XPS). IET spectra of nitrobenzoic acids and nitrophenols show that nitro groups of these compounds are reduced on the oxide and result in the corresponding amino compounds. In this conversion reaction, oxygen atoms of nitro group are consumed for the growth of the oxide layer and hydrogen atoms of the surface hydroxyl groups are used for the amidation reaction. The intermediate of the reaction is identified to the corresponding nitroso compounds from the XPS analysis.
  • Eiichi Miki, Kazuomi Ishimaru, Kunihiko Mizumachi, Tatsujiro Ishimori, ...
    1985 Volume 58 Issue 3 Pages 962-967
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    [CoL2nH2O (L=5-chloro-8-quinolinolate ion, n=4; L=5-nitro-8-quinolinolate ion, n=5) reacted with nitrogen monoxide in CH2Cl2 at ca. 253 K to give [CoL2(NO)] with NO group. [CoL2(NO)] reacted further with nitrogen monoxide in 10 v% pyridine–DMF at room temperature to give [CoL2(NO3)(py)]·nDMF·0.5py (L=5-chloro-8-quinolinolate ion, n=0; L=5-nitro-8-quinolinolate ion, n=1) with liberation of dinitrogen oxide. [CoL2nH2O also reacted with nitrogen monoxide in the pyridine–DMF to give the same nitrato complexes. In pyridine, [CoL2nH2O gave [CoL2(NO3)(py)]. In DMF, [CoL2nH2O reacted with nitrogen monoxide at room temperature to give [CoL2(NO)]·0.5H2O (L=5-chloro-8-quinolinolate ion) or [CoL2(NO2)(DMF)]·2H2O (L=5-nitro-8-quinolinolate ion).
  • Michio Nakashima, Masahiro Mikuriya, Yoneichiro Muto
    1985 Volume 58 Issue 3 Pages 968-973
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The benzonitrile adduct of copper(II) trichloroacetate, [Cu(Cl3CCOO)2(PhCN)]2, was prepared and characterized. The dimeric structure was confirmed by an X-ray structural determination. This compound crystallizes in the triclinic space group P\bar1 with a=12.780(1), b=16.064(1), c=10.130(1) Å; α=108.39(1), β=113.34(1), γ=81.07(1)°. The crystal consists of two crystallographically independent dimeric units. Both units have the familiar dimeric copper(II) acetate monohydrate structure with Cu–Cu distances of 2.731(1) and 2.732(1) Å. Magnetic susceptibility data in the range of 80–300 K are well represented by the usual dimer equation with a singlet-triplet energy separation of −2J=224 cm−1. The C≡N stretching frequency of benzonitrile in the compound shows an increase by 31 cm−1 from the free ligand value. On the basis of the X-ray crystallographic and IR spectroscopic results, the nature of the copper(II)–benzonitrile bond is discussed. For discussion magnetic and spectroscopic properties of some analogous nitrile adducts of copper(II) chloroacetates were also studied.
  • Yoshio Inoguchi, Shuko Okui, Kunio Mochida, Akiko Itai
    1985 Volume 58 Issue 3 Pages 974-977
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Reaktivitäten und chemische Eigenschaften von Diiodogermylen und Triphenylphosphindiiodogermylen wurden durch ihre Reaktionen mit Organolithium-Verbindungen oder Butadienen untersucht. Die Kristallstruktur von Triphenylphosphindiiodogermylen wurde röntgenographisch aufgeklärt.
  • Issei Nitta, Shinichiro Fujimori, Hiroaki Ueno
    1985 Volume 58 Issue 3 Pages 978-980
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The 17β-cyano-17α-hydroxyandrost-4-en-3-one can be prepared from androst-4-ene-3,17-dione in an excellent yield. This derivative can be converted into 17α-hydroxyprogesterone, an intermediate of corticosteroids.
  • Issei Nitta, Shinichiro Fujimori, Toshio Haruyama, Shinya Inoue, Hiroa ...
    1985 Volume 58 Issue 3 Pages 981-986
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    An efficient synthesis of 17α,21-dihydroxypregna-1,4-diene-3,20-dione 17,21-diacetate (10) from androsta-1,4-diene-3,17-dione (1), a biodegradation product of cholesterol, is described, which involves the ethynylation of the 17-ketone, the epimerization of the 17α-ethynyl group and conversion of the ethynyl group to the 20-keto pregnane. Overall yield is relatively high (about 54%) and 10 will be a potential intermediate for prednisolone.
  • Kiyoko Takamura, Satoshi Inoue, Fumiyo Kusu, Noboru Oyama
    1985 Volume 58 Issue 3 Pages 987-990
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The kinetics of electrocatalytic oxidation process of chlorpromazine (CPZ) at a pyrolytic graphite electrode in a phosphate solution was investigated by rotating disk voltammetry. The reactions involving regeneration process of CPZ through the disproportionation of reaction intermediates are proposed and the rate constants of the chemical reaction (kobsd), following the electrochemical oxidation of CPZ to the CPZ cation radical, were evaluated from the electrode rotation-rate dependence of the limiting currents obtained in the CPZ solution with and without phosphate. The proportional relations between the logarithm of kobsd and pH, and between kobsd and the concentration of H2PO4 were obtained.
  • Makoto Nitta, Akihiro Yi, Tomoshige Kobayashi
    1985 Volume 58 Issue 3 Pages 991-994
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The reaction of 4,5-polymethylene-substituted 2-isoxazolines, 3-phenyl-3a,5,6,7a-tetrahydro-4H-pyrano[3,2-d]isoxazole or 3-phenyl-3a,4,5,6a-tetrahydrofuro[3,2-d]isoxazole, with [Fe2(CO)9], [Fe(CO)5], or [Mo(CO)6] resulted in the formation of 5-hydroxy-1-phenyl-1-pentanone or 4-hydroxy-1-phenyl-1-butanone, via the N–O and C–C bond cleavage of the 2-isoxazoline ring and the subsequent hydrolysis. The similar reaction of 7a-morpholino- and 7a-(1-pyrrolidinyl)-3-phenyl-3a,4,5,6,7,7a-hexahydro-1,2-benzoisoxazoles undergoes the N–O bond cleavage and, the subsequent elimination of the amino group or the C-3a–C-7a bond fission. Although the reaction of 6a-morpholino- and 6a-(1-pyrrolidinyl)-3-phenyl-3a,4,5,6a-tetrahydro-4H-cyclopent[d]isoxazoles with [Mo(CO)6] undergoes the N–O bond cleavage, and the subsequent elimination of the amino group or the C-3a–C-6a bond fission, the reaction of those 2-isoxazolines with [Fe2(CO)9] proceeds very slowly. The mechanisms are proposed for these reactions.
  • Yuji Takikawa, Kazuaki Shimada, Katsuyuki Sato, Shinichi Sato, Saburo ...
    1985 Volume 58 Issue 3 Pages 995-999
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    3,5-Disubstituted 1,2,4-thiadiazoles 2 were prepared by reaction of thioamides 1 with DMSO in the presence of such an electrophilic reagent as 1-methyl-2-chloropyridinium iodide, benzoyl chloride, acetyl chloride, hydrochloric acid, or trimethylsilyl chloride in organic solvents at room temperature in high yields. Thiadiazoles 2 were also obtained by reaction of 1 with NBS at room temperature in high yields. Thioamide S-oxides reacted with electrophilic reagents at room temperature to give the corresponding thiadiazoles 2 in high yields.
  • Kazuhiko Saigo, Noriyuki Yonezawa, Kazuhiro Sekimoto, Masaki Hasegawa, ...
    1985 Volume 58 Issue 3 Pages 1000-1005
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    (±)-Anti head-to-head coumarin dimer was successfully resolved into a pair of optically active forms in good yields and in high optical purity by the fractional crystallization of both lactone-opened diamides with optically active 1-phenylethylamine followed by hydrolysis and relactonization. The absolute configuration of (−)589-anti head-to-head coumarin dimer was confirmed to be (3R,3′R,4R,4′R) by X-ray crystal structure analysis, which showed puckering of the cyclobutane ring (32.5°) and some short nonbonded distances (2.15–2.60 Å).
  • Kazuhiko Saigo, Kazuhiro Sekimoto, Noriyuki Yonezawa, Fumio Ishii, Mas ...
    1985 Volume 58 Issue 3 Pages 1006-1009
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The enantiomeric excess of chiral amines was successfully determined by 1H NMR spectral and/or HPLC analysis of the diastereomeric diamides derived from optically active anti head-to-head coumarin dimer and the amines by lactone-ring-opening reaction without any condensing agent. This procedure also proved to be applicable to chiral alcohols.
  • Keisaku Kimura, Shinsuke Nakajima, Katsumi Niki, Hiroo Inokuchi
    1985 Volume 58 Issue 3 Pages 1010-1012
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Macroscopic redox potentials of tetrahemoprotein, cytochrome c3 from D. vulgaris, Miyazaki strain, were derived from 400 MHz 1H NMR measurements. The formal potential, E1o′, was determined to be −0.245±0.005 V vs. NHE compared with a value of −0.240 V obtained electrochemically. The distributions of the intermediate states from the NMR spectra during a redox titration are in good agreement with those previously determined by electrochemistry.
  • Norio Nishimura, Takushi Motoyama
    1985 Volume 58 Issue 3 Pages 1013-1018
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The proton/deuteron transfer reaction of Leucocrystal Violet(LCV) with tetracyanoethylene(TCNE) and chloranil(CA) in various solvents has been followed spectrophotometrically. It was found that the reaction proceeds slower in polar solvents such as acetonitrile and acetone than in less polar solvents such as chloroform and 1,2-dichloroethane. The rate is remarkably accelerated by pressure indicating probably a substantial polarity increase in the rate processes. The formation of CT complexes was observed at low temperatures. Their nature is presumed to be similar to that of a complex formed by the reaction of CA with N,N-dimethyl-p-toluidine(DMT), and the latter is discussed in connection with the reaction rate of the LCV–TCNE and LCV–CA systems. A possible reaction path is proposed.
  • Shigeyoshi Miyagishi, Seiichi Matsumura, Kazuhiko Murata, Tsuyoshi Asa ...
    1985 Volume 58 Issue 3 Pages 1019-1022
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The melting characteristics of N-acyl amino acids were examined using a differential scanning calorimeter (DSC). The melting-point temperature of N-dodecanoyl L-amino acid increased with the size of its amino acid residue, while the order was opposite for the DL-amino acids. The racemic derivatives formed racemic compounds in their solid states. Each N-dodecanoyl L-amino acid had a larger enthalpy and entropy-of-fusion than its racemic isomer. Differences in the thermodynamic quantities between the optically active and racemic isomers were larger for N-dodecanoylvaline and -leucine compared with those of N-dodecanoylalanine. A mixture of these molecules were also studied. Each racemic isomer of N-dodecanoylalanine and -leucine partly formed a racemic pair in the liquid state.
  • Masafumi Yoshida, Shinsuke Yamaguchi, Noriyuki Sakamoto, Shizuo Arichi
    1985 Volume 58 Issue 3 Pages 1023-1028
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The relationships between the weight-average molecular weight Mw and the intrinsic viscosity [η] of poly(2-vinylpyridine) [P2VP] in benzene and methyl alcohol at 25 °C, were investigated by the use of fractions with molecular weights ranging from 2.1×103 to 2.3×104. The exponent ν in the Mark-Houwink-Sakurada equation, [η]=K0Mwν, was 0.5 in both solvents when Mw was lower than about 104. A constant K0 was approximately in accord with Flory’s Kθ value for ordinary high-molecular-weight P2VP, obtained earlier in respective solvents. By measuring [η] for these low-molecular-weight fractions in several solvents at different temperatures, the temperature coefficients of an unperturbed dimension, dln\barr20dT, of this polymer were estimated and averaged to be −2.3×10−3 K−1. These are quite different from the positive values calculated from the Kθ’s by Dondos et al. which were estimated using the extrapolation method for non-θ-solvents. Our results were further corroborated after adding a Kθ value which was directly determined at another θ-state; i.e. in toluene at 63.7 °C, to that in benzene at 16.2 °C published earlier, which was found from phase-separation experiments in this work.
  • Hiroshi Shioyama, Akihiro Takami, Noboru Mataga
    1985 Volume 58 Issue 3 Pages 1029-1032
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Behaviors of excited [Ru(bpy)3]2+ bound to anionic molecular assemblies such as polymer electrolytes, vesicles and micelles together with electron-acceptor quencher MV2+ have been investigated by measurements of [Ru(bpy)3]2+ luminescence quenching and radical yields in electron-transfer quenching using a dye laser photolysis apparatus. Quenching behavior characteristic to each molecular assembly has been observed. A remarkable enhancement of quenching was observed in the presence of poly(vinyl sulfate). Such an effect was observed also in sodium dihexadecyl phosphate solution though it is less pronounced. However, no such specific quenching behavior was observed in sodium dodecyl sulfate micellar solution.
  • Isao Sanemasa, Toyohisa Kobayashi, Toshio Deguchi
    1985 Volume 58 Issue 3 Pages 1033-1036
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Formation constants of cyclodextrin (CyD) inclusion complexes with iodine were determined by measuring solubilities of iodine vapor in water. The formation constants at 25 °C are 8.3×103 (α-CyD), 1.0×102 (β-CyD), and 13 dm3 mol−1 (γ-CyD). The temperature dependence of α-CyD–I2 complexation was studied. ΔH and ΔS, being 9.52 kJ mol−1 and 107 J K−1 mol−1 at 25 °C, respectively, are both largely dependent on temperature even within a rather small temperature range 15–35 °C studied. For the complexation with α-CyD, contribution of dehydration of iodine was estimated. The method proposed here is useful to study the formation of CyD association complexes with such substrates as are slightly soluble in water and easily vaporize from the aqueous phase.
  • Hitoshi Hoshino, Takao Yotsuyanagi
    1985 Volume 58 Issue 3 Pages 1037-1040
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The nickel(II) complex of 4-(2-pyridylazo)resorcinol (PAR, H2L) is known to show somewhat anomalous and complicated behavior in solution. In this regard, the solubility and the synergistic extraction equilibria of the above complex are studied in connection with acid dissociation reactions. The intrinsic solubility and the acid dissociation constants are determined to be, S0=[[Ni(HL)2]]=10−6.2±0.1 mol dm−3, Ka1=[[Ni(HL)L]][H+][[Ni(HL)2]]−1=10−6.2±0.1, and Ka2=[[NiL2]2−][H+][[Ni(HL)L]]−1=10−7.1×0.1, respeactively in the solution with the ionic strength of 0.10 (Na2SO4) at 298 K. Using the above constants, the extraction constant of the neutral complex with trioctylphosphine oxide (TOPO) into chloroform is evaluated as Kex=[[Ni(HL)2(TOPO)2]]o[[Ni(HL)2]]−1[TOPO]o−2=103.1±0.2, where the subscript o denotes the organic phase. An equilibrium diagram for the nickel(II)–PAR complexes is proposed.
  • Tsuneo Matsuda, Yo Sasaki, Hiroshi Miura, Kazuo Sugiyama
    1985 Volume 58 Issue 3 Pages 1041-1042
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Basic properties of MgO doped with NaOH, KOH, and Li2CO3 which was calcined at 550, 700, and 900 °C in air were examined. The basicity of the catalysts was determined from the irreversible amount of adsorption of phenol and BF3, followed by evacuation at room temperature (for both adsorbates), 100, 200, and 300 °C (for phenol) after adsorption at room temperature. A good correlation was observed between the amount of phenol remained after evacuation at higher temperature than 200 °C and that of BF3. By doping of 1 wt% of alkali metal compounds in MgO the isomerization activity of 1-butene was enhanced, but by 10 wt% the activity remarkably decreased.
  • Hiroshi Miura, Toshiyuki Narita, Makoto Haruta, Kazuo Sugiyama, Tsuneo ...
    1985 Volume 58 Issue 3 Pages 1043-1044
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    A novel method is proposed to inspect the oxygen content of the helium used as the carrier gas in pulse-adsorption experiments. The oxygen is first adsorbed on Pt/SiO2 catalyst and then titrated by CO pulses. This method is very simple and requires only a conventional pulse-adsorption system.
  • Jun-ichi Aihara
    1985 Volume 58 Issue 3 Pages 1045-1046
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Two apparently different but physically identical formulas were presented to evaluate bond currents (i.e., ring currents in popular terminology) induced in a polycyclic conjugated system. They are applicable to all kinds of planar conjugated systems.
  • Yonezo Maeda, Yoshimasa Takashima, Kiyotake Ishida
    1985 Volume 58 Issue 3 Pages 1047-1048
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The Mössbauer spectra for danalite have been examined in the temperature range 4.2 to 321 K. The strong temperature dependencies of the Mössbauer parameters are explained on the basis of a ligand field at a tetrahedral site for iron.
  • Yukio Sasaki, Kazuya Abe, Masao Takizawa
    1985 Volume 58 Issue 3 Pages 1049-1050
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The thermodynamic constants for the formation of halogenocadmium complexes in N,N-dimethylformamide (DMF) and propylene carbonate (PC) were calculated by potentiometric titration. The differences in the order of the stability among the halide ions (X) for CdX42− in nonaqueous solvents and water were found to be dependent mainly on the enthalpy changes of transfer from water to DMF and PC for the formation of CdX42−.
  • Akira Ono, Fujio Peter Okamura
    1985 Volume 58 Issue 3 Pages 1051-1052
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    A new phase with chemical formula Zr(OH)PO4 was prepared above 1.5 GPa using a high pressure apparatus. Stability field of the compound was investigated, and X-ray study for a single crystal revealed that it is orthorhombic with space group Cmca or C2ca. The X-ray data are similar to those of Zr2O(PO4)2.
feedback
Top