Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 54 , Issue 3
Showing 1-50 articles out of 72 articles from the selected issue
  • Masao Sakurai, Tsuyoshi Komatsu, Tsurutaro Nakagawa
    1981 Volume 54 Issue 3 Pages 643-647
    Published: 1981
    Released: June 02, 2006
    JOURNALS FREE ACCESS
    The apparent molal adiabatic compressibilities of NaCl, KCl, NaBr, and KBr in water have been measured in the concentration range from 0.01 to 1 mol kg−1 at 5, 25, and 45 °C. The results have been fitted to a Redlichtype equation: φKsKs°+SKsc1⁄2+BKsc. The limiting slope, SKs, was found experimentally as 5.6×10−4 at an ordinary temperature. Convenient equations for the conversion of adiabatic to isothermal compressibilities have been derived; the limiting slope for isothermal compressibility, SKT, should be larger than SKs at all the temperatures studied. The value of SKs determined experimentally has been compared with that predicted from the SKT values calculated by Mathieson and Conway, by Millero, and by Bradley and Pitzer.
  • Toshiyuki Matsumoto, Yoshio Matsunaga
    1981 Volume 54 Issue 3 Pages 648-653
    Published: 1981
    Released: June 02, 2006
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    The electromotive force (emf) of a solid-state galvanic cell, Ag|AgI|PT–In, where PT–In is the phenothiazine-iodine complex, was examined as functions of the composition, n, and also of the temperature. Below n=2.5, a value of 616 mV was obtained at 25 °C. The emf increases stepwise to 620 mV at n=2.5 in conformity with the formation of a complex cation radical pentaiodide, as established by our earlier work. A continuous increase up to 649 mV was found before n=3, indicating the appearance of a nonstoichiometric phase covering the range from n=2.8 to 3. The upper limit of the existence region exactly corresponds with the minimum in the resistivity-composition isotherm. Similar studies with benzo[a]- and benzo[c]phenothiazines revealed the formation of three or four distinct nonstoichiometric complexes in each system. The Gibbs energy, enthalpy, and entropy of cell reactions and complex formation reactions are presented. The stability of the iodine complexes was found in the following order: benzo[a]phenothiazine>benzo[c]phenothiazine>phenothiazine.
  • Masaru Mitsuishi, Yuzoh Yamaguchi
    1981 Volume 54 Issue 3 Pages 654-656
    Published: 1981
    Released: June 02, 2006
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    The mean activity coefficients of sodium salts of 1-amino-4-alkylaminoanthraquinone-2-sulfonic acid (alk= Me(MAS), Et, n-Pr, or n-Bu (n-BAS)) in aqueous solutions ranging in concentration from 10−3 to 10−2 mol kg−1 have been determined by means of isopiestic measurements at 50 and 60 °C respectively. It has been found that the mean activity coefficients of these dyes are much smaller than unity, the coefficients of MAS being the largest, and those of n-BAS, the smallest. The coefficients have been found to decrease with an increase in the dye concentration. An examination of the results obtained by Miliceivic treatment suggests that the MAS exists as dimer or trimers, and the other dyes, as tetramers, at 60 °C.
  • Akio Furusaki, Shinsei Gasa, Ry\={u}z\={o} Ikeda, Takeshi Matsumoto, N ...
    1981 Volume 54 Issue 3 Pages 657-660
    Published: 1981
    Released: June 02, 2006
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    The molecular structure of grayanotoxin XVIII C20H28O4, has been determined by means of X-ray crystal analysis. The crystals are monoclinic, with two molecules in a unit cell with dimensions of a=9.592, b=11.414, c=8.180 Å, and β=93.21°; the space group is P21. 1484 unique intensity data were collected on a four-circle diffractometer with Ni-filtered Cu Kα radiation. The structure was solved by the Monte Carlo direct method, using the 20 strongest reflections as the starting set; the 25th random-phase set led to the correct solution. The R value reached 4.6% by block-diagonal least-squares refinements. The structure thus obtained corresponds to 3-dehydrograyanotoxin VII. The C-ring takes a boat conformation. The force-field calculations suggest that this energy loss is probably compensated for by the stabilization of the B-ring conformation. The crystal consists of hydrogen-bonded molecular layers parallel to the (100) plane.
  • Osamu Ikeda, Katsuhiko Tsuura, Hideo Tamura
    1981 Volume 54 Issue 3 Pages 661-668
    Published: 1981
    Released: June 02, 2006
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    In order to know the role of aromatic ring on the electrode kinetics, d. c. polarogram of Eu(III) ion was measured in the presence of 1,4-benzenedimethanol (1,4-BDM). The effect of the adsorption has been discussed by correlating the kinetic data to the adsorption behaviors of 1,4-BDM estimated from the electrocapillary curves. At the standard potential of Eu(III)/Eu(II) (−0.600 V vs. SCE), 1.4-BDM on the electrode changed its orientation from horizontal to vertical with an increase in the coverage. Both orientations showed an inhibition effect for the electroreduction of Eu(III) ion. When the coverage due to the horizontal orientation is less than 0.8, the inhibition was interpreted by an additional energy to deform the surface layer. On the other hand, the inhibition at full coverage due to both the horizontal and the vertical orientations was interpreted by the tunneling probability through the adsorbed layer differed in the thickness.
  • Kazutoshi Iwamoto, Manabu Seno
    1981 Volume 54 Issue 3 Pages 669-673
    Published: 1981
    Released: June 02, 2006
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    The behavior of a new chemical reaction model was studied and the existence of hard oscillations was confirmed. This chemical reaction model is useful because it is easy to apply to investigations of the behavior of a chemically oscillating system surrounded by membranes or in a well-stirred continuous flow reactor. The latter was discussed relating to the chaotic oscillations due to the Belousov-Zhabotinskii reaction in a well-stirred continuous flow reactor reported by Schmitz et al.
  • Kazutoshi Matsumoto, Toshiyuki Sata
    1981 Volume 54 Issue 3 Pages 674-677
    Published: 1981
    Released: June 02, 2006
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    The system of calcium oxide and water vapor was studied using the transpiration method. Under the conditions of a temperature range from 1678 to 2016 K and PH2O values from 1.2×10−2 to 4.7×10−1 atm, the predominant reaction in this system was found to be CaO(s)+H2O(g)=Ca(OH)2(g). The standard Gibbs free energy of the reaction is given by this equation: ΔGr°=(61300±820)−(12.8±0.48)T (cal/mol) in the present temperature range. From the thermochemical cycle, the dissociation energy, D0°(Ca–(OH)2), was estimated to be 206.4 kcal/mol.
  • Akiko Sibata, Makoto Takahasi, Shinichi Ohno, Hitoshi Mikuni
    1981 Volume 54 Issue 3 Pages 678-684
    Published: 1981
    Released: June 02, 2006
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    The reaction of metastable Ar atoms with propylene was studied in a discharge flow system. The major product is ethylene, although ethane, propane and butadiene are also identified as minor products. Within a limited range of propylene concentration the yield of ethylene is proportional to the concentration of propylene. Competitive quenching methods using mixtures of propylene and N2O or CO2 provided a rate constant of (8.4±0.3)×10−10 cm3 molecule−1 s−1 for the reaction of metastable Ar atom with propylene to yield ethylene. The assumption of a radical mechanism for the main reaction is consistent with the results of competitive quenching, radical scavenger and spin trapping experiments. Measurements of ion current in the reaction mixtures allow an estimation that ionic species contribute less than 2% to the reaction path leading to the formation of ethylene. The metastable Ar atom reaction was also compared to the direct and mercury-sensitized photolysis of propylene.
  • Shun-ichi Ishikawa, Junko Nakamura, Saburo Nagakura
    1981 Volume 54 Issue 3 Pages 685-686
    Published: 1981
    Released: June 02, 2006
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    The mechanism of photodissociation of [2.2]paracyclophane in glassy solvent at 77 K was studied. It is concluded that the dissociation of the CH2–CH2 bridge occurs from higher triplet states (Tn) via the lowest triplet state as an intermediate. The efficiency of the reaction depends on the characters of Tn states; high from the locally excited state, and low from the charge-transfer state.
  • Kimihiko Hara, Yoshikazu Katou, Jiro Osugi
    1981 Volume 54 Issue 3 Pages 687-691
    Published: 1981
    Released: June 02, 2006
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    The compressive behavior of adamantane and its secondary monosubstituted derivatives; adamantanone, 2-methyladamantane, and 2-bromoadamantane was measured at various temperatures in a piston-cylinder apparatus. A first-order solid-solid phase transition was found under pressure in each system. The transition pressures, the equilibrium pressures, the volume changes, and the entropy changes for the transition were determined. The compression data for the low pressure phases were fitted to an equation of the form −ΔVV0=a0+a1P+a2P2. The effects of substituent groups on the entropy changes of the transitions of these molecular crystals were discussed.
  • Michio Matsumura, Kenro Mitsuda, Nobuyuki Yoshizawa, Hiroshi Tsubomura
    1981 Volume 54 Issue 3 Pages 692-695
    Published: 1981
    Released: June 02, 2006
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    The photocurrents in zinc oxide and titanium dioxide electrodes sensitized by anionic xanthene dyes (Eosine Y, Phloxine B, Erythrosine, and Rose Bengal) and metal tetraphenylporphines were studied in aqueous solutions. The quantum efficiencies of the photocurrents sensitized by anionic xanthene dyes were unaffected by substitution of the dye with various halogen atoms, while those sensitized by the tetraphenylporphines were affected by changing the central metal. It is concluded from these results that the electron injection from the excited xanthene dyes to the semiconductor electrodes is a process so rapid (<<0.1 ns) that no internal quenching processes can compete with it, while that from the tetraphynelporphines is relatively slow competing with the internal deactivation processes. It is also concluded that the electron back transfer from the semiconductor conduction band to the oxdized dye decreases the sensitization efficiency.
  • Naoto Yamamoto, Shoichiro Tonomura, Tsugufumi Matsuoka, Takashi Amamiy ...
    1981 Volume 54 Issue 3 Pages 696-699
    Published: 1981
    Released: June 02, 2006
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    The work function of silver oxide (Ag2O) decreased by as much as 0.8 eV on exposure to 2-propanethiol [(CH3)2CHSH]. The change in work function was irreversible at room temperature, and proportional to the amount of thiol in case where the partial pressure is low, but reversible at 200 °C. The conductivity of the Ag2O disk showed no substantial change by exposure to thiol. From the infrared absorption spectral studies, it was found that the thiol reacted with the silver oxide forming a (CH3)2CH–S–Ag group on the surface. The relationship between the work function and the chemical processes occurirng at the solid surface is discussed.
  • Yoshio Shijo, Tokuo Shimizu, Kaoru Sakai
    1981 Volume 54 Issue 3 Pages 700-702
    Published: 1981
    Released: June 02, 2006
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    Vanadium(V) can be quantitatively extracted from an aqueous solution into carbon tetrachloride as the ion-association system formed between its Pyrocatechol Violet complex anion and tridodecylethylammonium salt. The optimum pH range for the extraction is around 5. The ternary complex has an absorption maximum at 570 nm in the organic layer. The distribution ratio and the molar absorptivity are 1.78×102 and 4.0×104 mol−1 cm−1 respectively. Omitting the other adducts which may be combined with vanadium, the composition of the ternary complex is estimated to be V(PV)2(R3R′N)2. The extraction constant is given by logKex=12.58. The interference of foreign ions is discussed, too.
  • Hiroshi Kishi
    1981 Volume 54 Issue 3 Pages 703-708
    Published: 1981
    Released: June 02, 2006
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    The relative sensitivity coefficients for negative ions of 15 elements contained in compressed aluminium powder electrodes were measured by spark source mass spectroscopy. The relative sensitivity coefficients for the halogens and group VIB elements were found to be the largest, the difference of relative sensitivity coefficients between the elements being larger than in the case of positive ion relative sensitivity coefficients. The logarithm of the relative sensitivity coefficients of negative ions are linearly correlated to the electron affinities of the elements.
  • Tooru Yoshida
    1981 Volume 54 Issue 3 Pages 709-712
    Published: 1981
    Released: June 02, 2006
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    The X-ray photoelectron spectra of the copper(II) and nickel(II) complexes of five o-hydroxy azo compounds were measured. The N(1s) electron spectra of the complexes of 1-phenylazo- and 1-(1-naphthylazo)-2-naphthols showed the presence of only one kind of nitrogen atom, suggesting an equalization in the electron densities on the two nitrogen atoms of an azo group. Such equalization was observed also in the complexes of 1-(8-quinolylazo)-2-naphthol. The N(1s) spectra of the complexes of 1-(2-pyridylazo)- and 1-(2-thiazolylazo)-2-naphthols, on the other hand, showed the presence of three kinds of nitrogen atoms, suggesting the non-equalization of the two nitrogen atoms of an azo group. These results were explained mainly on the basis of the mode of ligand coordination and the resonance structure of the sodium salt of the ligand. Furthermore, the relation between the structures of the complexes and the O(1s) chemical shifts was discussed.
  • Koji Okamoto, Masahide Noji, Yoshinori Kidani
    1981 Volume 54 Issue 3 Pages 713-718
    Published: 1981
    Released: June 02, 2006
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    Six-membered platinum(II) complexes of 2-(aminomethyl)cyclohexylamine (=amcha), whose four isomers are (1R,2R)-, (1S,2S)-, (1R,2S)-, and (lS,2R)-amcha, were synthesized. The conformations of [Pt(en)(lS,2S-amcha)]Cl2, [Pt(NH3)2(1S,2R-amcha)]Cl2, [Pt(en)(1R,2R-amcha)]Cl2, and [Pt(NH3)2(1R,2R-amcha)]Cl2 were determined by 1H-NMR, 13C-NMR, and CD spectra. It is proposed that [Pt(en)1S,2S-amcha)]Cl2 and [Pt(NH3)2(1S,2S-amcha)]Cl2 take a fixed chair form with a dihedral angle (Pt–N–C(1)–C(6)) of 180°, while [Pt(en)(1S,2S-amcha)]Cl2 and [Pt(NH3)2(1S,2S-amcha)]Cl2 are interconverting between two chair forms.
  • Kazuko Ogino, Hitoshi Seki
    1981 Volume 54 Issue 3 Pages 719-721
    Published: 1981
    Released: June 02, 2006
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    The base hydrolysis of cis-[CoX(etaH)(en)2]2+(X=Cl or Br, etaH=2-aminoethanol, en=ethylenediamine) has been studied. The hydrolysis results in the formation of [Co(eta)(en)2]2+ (≈35%) and [Co(OH)(etaH)(en)2]2+ (≈65%) at I=1.0 (KNO3), 25 °C, the product ratio being independent of the pH. The base hydrolysis has also been studied in the presence of sodium azide.
  • Yoshinori Sugitani, Masahisa Fujinami
    1981 Volume 54 Issue 3 Pages 722-724
    Published: 1981
    Released: June 02, 2006
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    The strong pleochroic band of brown tourmaline at around 24000 cm−1 in the E⊥ c photoacoustic spectra was assigned to d-d(6A14A1, 4E) transition of Fe and to charge transfer of Ti, that in the E//c spectra being entirely assigned to charge transfer of Ti. The analysis of the photoacoustic signal intensity vs. chopping frequency gave the thermal diffusivity constant of tourmaline as α=0.15 cm2/s.
  • Kazuo Kashiwabara, Isamu Kinoshita, Tasuku Ito, Junnosuke Fujita
    1981 Volume 54 Issue 3 Pages 725-732
    Published: 1981
    Released: June 02, 2006
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    Bis(acetylacetonato)cobalt(III) complexes containing a variety of 2-aminoalkylphosphines, NH2CH2CH2P(C6H5)2, (CH3)2NCH2CH2P(C6H5)2, (S)-NH2CH(CH3)CH2P(C6H5)2, rac-NH2CH2CH2P(CH3) (C6H5), (R)-NH2CH2CH2P(C4H9)(C6H5), and NH2CH2CH2P(CH3)2, and a diphosphine, (C6H5)2PCH2CH2P(C6H5)2 were prepared and resolved (or separated) into optical isomers by SP-Sephadex column chromatography. Absorption, circular dichroism, and 1H and 13C NMR spectra of the new complexes were measured and the results compared with those of the related complexes. Positions of the 2-aminoalkylphosphine and the related ligands in the spectrochemical series were as follows; CN>NH2CH2CH2P(CH3)2>(C6H5)2PCH2CH2P(C6H5)2>NH2CH2CH2P(CH3) (C6H5)(Remark: Graphics omitted.)NH2CH2CH2P(C4H9)(C6H5)>NH2CH(CH3)CH2P(C6H5)2(Remark: Graphics omitted.)NH2CH2CH2P(C6H5)2(Remark: Graphics omitted.)NH2CH2CH2NH2>(CH3)2NCH2CH2P(C6H5)2. For the 13C NMR spectra, all the signals including those due to two diastereotopic phenyl groups on a phosphorus atom were assigned, and the chemical shifts and the coupling constants were determined. The methyl and carbonyl carbons which are trans to a phosphorus atom give a doublet signal due to four-bond (4J(C,P)=6–7 Hz) and three-bond (3J(C,P)=2–3 Hz) couplings, respectively, through a cobalt(III) ion.
  • Shuzo Tokunaga, Kitoshi Uematsu, Yoshinobu Nagawa
    1981 Volume 54 Issue 3 Pages 733-737
    Published: 1981
    Released: June 02, 2006
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    The stability of calcium silicon in aqueous solutions was studied by determining dissolution rates of Ca and Si at a constant pH. Calcium silicon was found to be fairly stable in solutions of pH 3.0–8.0, at most less than 2.8%of Ca and 0.5% of Si being dissolved after 24 h. In a strong acid solution of pH 2.5 or less the dissolution rates of Ca and Si considerably increased. Ca dissolution reached a plateau and the whole amount of Ca did not dissolve even in a 3.0-mol dm−3 HCl solution, while Si dissolution continued to increase. Calcium silicon apparently reduces metal ions to the elemental state for metal ions having higher standard electrode potentials than Cd(II) ions except Ni(II) and Co(II) ions. For Ag(I) ions, nitrate ions interfere with the reduction, but chloride ions favor it. Reduction of Cr(VI) and Fe(III) ions terminated at the stage of Cr(III) and Fe(II). Pb(II), Cu(II), and Hg(II) ions were reduced to the metals, the acidity of the solution and the metal ion concentration not affecting the reduction. Calcium silicon is effective also for low-solubility compounds of these elements in suspension.
  • Makoto Watanabe, Makoto Matsuura, Tamotsu Yamada
    1981 Volume 54 Issue 3 Pages 738-741
    Published: 1981
    Released: June 02, 2006
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    The effect of cations on the rate of hydrolysis of pyro- and triphosphates was studied by adding metal chloride to aqueous solutions of the phosphates. The concentrations of the phosphates and metal chlorides were 0.025 and 0.1 mol dm−3 respectively. Alkali metal, alkaline earth metal, aluminium, and some transition-metal (Mn(II), Co(II), Ni(II), Cu(II), and Zn(II)) cations retarded the hydrolysis of the phosphates in acidic media. The following sequence of efficiency resulted:
    trivalent>bivalent>univalent.
    The efficiency of elements within one group of the periodic table decreased from top to bottom. On the other hand, in alkaline solutions, alkali metal cations accelerated the hydrolysis of the phosphates and the catalytic effectiveness decreased with an increase in the ionic radius.
  • Yoshinao Oosawa, Toshiya Kumagai, Susumu Mizuta, Wakichi Kondo, Yoshio ...
    1981 Volume 54 Issue 3 Pages 742-748
    Published: 1981
    Released: June 02, 2006
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    The decomposition of hydrogen iodide serves as the hydrogen-evolution step in several thermochemical water-splitting cycles, including the Magnesium–Iodine cycle. A kinetic analysis of the catalytic decomposition of hydrogen iodide has been carried out by the use of a flow method at 500–700 K. The platinum-supported active carbon catalyst (1 wt%) and the active carbon catalyst which have been found effective in the research reported previously, are used as the catalysts. The contact time-conversion relationships for both the catalysts are simulated successfully on the basis of an assumed reaction scheme. The influence of water vapor on the rate and the equilibrium of the decomposition of hydrogen iodide is negligibly small. The inhibition effect of iodine on the rate of the decomposition of hydrogen iodide over the platinum-supported active carbon catalyst is remarkable below 550 K.
  • Isao Tomita, Kenkichi Iwase, Kazuhiko Saito, Yoshiyuki Sugiyama
    1981 Volume 54 Issue 3 Pages 749-753
    Published: 1981
    Released: June 02, 2006
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    Ion-exchange studies of crystalline zirconium titanium phosphate with variable zirconium-to-titanium mole ratios have been extended to sodium-ion exchange on the exchangers with Zr-to-Ti mole ratios of 0.37 and 0.61, and to lithium and potassium ion exchange on the exchanger with a Zr-to-Ti mole ratio close to unity. In the sodium-ion exchange, a mono-sodium phase formed up to about a half of the exchange; then a disodium phase with a different amount of water of crystallization formed. In the lithium-ion exchange, the reaction proceeded with the formation of fully exchanged phases whose water content varied depending upon the environment in which the exchanger was placed during or after the reaction. The exchange amount of potassium ions was much less than that of sodium or lithium ions, and the ion exchange proceeded in parallel with an extensive hydrolysis of the exchanger. The half-exchanged phase could not be confirmed in this case. For the three alkali metal ions studied, the selectivity series was found as a function of loading, i.e., within the range of the load from 0 to 1.3 meq/g, the selectivity is in the order of Na+>K+>Li+, between 1.3 and 4.5 meq/g, it is Na+>Li+>K+, and above 4.5 meq/g loading, it turns out to be Li+>Na+>K+.
  • Kazushi Hirota, Yasutoshi T. Hasegawa
    1981 Volume 54 Issue 3 Pages 754-756
    Published: 1981
    Released: June 02, 2006
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    Phase relations in the system PbO–PbSiO3 were determined at temperatures above 650 °C. Two new lead silicate phases, Pb5SiO7 and Pb11Si3O17 were found to be stable. The former melts incongruently at 733±1 °C to solid PbO plus liquid, and decomposes below 702±1 °C. The latter melts congruently at 728±1 °C. The compound Pb4SiO6, which has been accepted as stable, could not be confirmed.
  • Yoshinori Kitaoka
    1981 Volume 54 Issue 3 Pages 757-760
    Published: 1981
    Released: June 02, 2006
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    Paper electrophoretic migrations of adenine, adenosine, and adenosine nucleotides as a function of pH-values of various supporting solutions have been studied. The buffering capacity of the supporting solution played an important role in the migration and is discussed along with the electroosmosis. The Rf-values of adenines in the supporting solutions are also presented.
  • Ken-ichi Onuma, Asao Nakamura
    1981 Volume 54 Issue 3 Pages 761-765
    Published: 1981
    Released: June 02, 2006
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    The molecular structure of the title compound has been determined from three-dimensional X-ray diffraction data. The crystal belongs to the triclinic system: P\bar1, a=11.488(2), b=18.163(2), c=10.998(2)Å, α=101.70(2), β=118.29(1), γ=85.32(3)°, Z=2. The structure has been refined by block-diagonal least-squares techniques using 3749 non-zero reflections to the final R value of 0.067. The rhodium atom is coordinated in a slightly distorted square-planar geometry by the bisphosphine and the diene ligand, with average Rh–P and Rh–C distances of 2.301(2) and 2.26(1)Å, respectively. The seven-membered chelate ring takes a distorted boat conformation, and the two phenyl groups of diphenylphosphine are arranged in a face-edge manner and those of the other diphenylphosphine are in a helical arrangement like a propeller, viewed from cycloocta diene.
  • Masaru Sato, Seiji Ebine, Kazumi Nishijima, Josuke Tsunetsugu
    1981 Volume 54 Issue 3 Pages 766-770
    Published: 1981
    Released: June 02, 2006
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    Biphenylene-2,3-quinone reacts with diazomethane in the presence of boron trifluoride etherate to give 7-hydroxy-6H-benzo[3,4]cyclobuta[1,2]cyclohepten-6-one (5) and its boron difluoride chelate. The latter is convertible quantitatively into the former. Compound 5 has a reduced troponoid character due to fusion of the benzocyclobutadiene ring. Tautomerism of the tropolone ring in 5 seems to be imposed exclusively to one of the tautomers. Protonation of 5 gives a tropylium ion whose positive charge is partially localized. Bromination, nitration, and azo-coupling of 5 give only 7-substituted products. The reaction of 5 with maleic anhydride gives the Diels-Alder adduct in good yield.
  • Hitomi Suzuki, Ichiro Hidaka, Akemi Iwasa, Tadashi Mishina, Atsuhiro O ...
    1981 Volume 54 Issue 3 Pages 771-775
    Published: 1981
    Released: June 02, 2006
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    The reaction of 2,5-dimethylthiophene with copper(II) nitrate in acetic anhydride gave 3-nitro-2,5-dimethyl-thiophene and 2,5-dimethyl-3-(5-methyl-2-thenyl)thiophene as major isolable products. The treatment of 3,4-dibromo-2,5-dimethylthiophene with nitric acid (d=1.5) in dichloromethane in the presence of a catalytic amount of sulfuric acid afforded 3,4-dibromo-5-methyl-2-(nitrooxymethyl)thiophene, which, on thin-layer chromatog-raphy over silica gel using hexane as the eluant, underwent a partial novel coupling reaction through the loss of one methylene carbon atom, thus giving 3,3′,4,4′-tetrabromo-5,5′-dimethyldi-2-thienylmethane along with the expected 3,4-dibromo-2-hydroxymethyl-5-methylthiophene and bis(3,4-dibromo-5-methyl-2-thenyl) ether.
  • Hiroshi Ishikawa, Teruaki Mukaiyama, Shigeru Ikeda
    1981 Volume 54 Issue 3 Pages 776-780
    Published: 1981
    Released: June 02, 2006
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    The reaction of dialkyl acetals derived from α,β-unsaturated aldehydes with Grignard reagents using TiCl4in THF afforded the cross coupling products, allyl ethers, in high yields. The TiCl4-promoted reaction of alkyl 2,4-dichlorophenyl acetals, synthesized from 3,4-dihydro-2H-pyran or ethyl vinyl ether and 2,4-dichlorophenol, with Grignard reagents in THF at low temperature afforded the corresponding unsymmetrical ethers in high yields. When alkyl 2,4-dichlorophenyl acetals, synthesized from aromatic aldehyde or vinyl ethers and 2,4-dichlorophenol, were treated with Grignard reagents in benzene or toluene at room temperature in the absence of TiCl4, the cross coupling reaction took place and the corresponding ethers were isolated in good yields.
  • Takayuki Usui, Tsutomu Tsuchiya, Hamao Umezawa, Sumio Umezawa
    1981 Volume 54 Issue 3 Pages 781-786
    Published: 1981
    Released: June 02, 2006
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    3″-Deoxydihydrostreptomycin active against resistant bacteria was prepared from dihydrostreptomycin (DHSM). The key intermediate in this synthesis is a protected derivative of DHSM in which all hydroxyl groups except the 3″-hydroxyl group are protected, namely, 2″-N-(benzyloxycarbonyl)-2,5,6-tris(O-tetrahydropyran-2-yl)-3′,3a′:4″,6″-bis(O-p-methylbenzylidene)-1,3-di-NG-tosyldihydrostreptomycin. 3″-Deoxygenation was successfully performed by 3″-O-imidazolylthiocarbonylation followed by treatment with tributylstannane. The Δ[M]TACu value of the synthetic 3″-deoxydihydrostreptomycin supports the structure.
  • Yasuhiro Yamamoto, Hiroshi Yamazaki
    1981 Volume 54 Issue 3 Pages 787-789
    Published: 1981
    Released: June 02, 2006
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    The reactions of RNC with CH2R1R1(R=2,6-Me2C6H3; R1, R2=COOMe, COOEt, CN) in the presence of Co2(RNC)8 or Co2(CO)8 gave cyclic compounds in a 4:1 molar ratio. Co2(RNC)8 also catalyzed CH2(CN)2 to give a pyridine derivative.
  • Toyokazu Horii, Shunichi Kawamura, Takeshige Nakabayashi, Yasuo Abe
    1981 Volume 54 Issue 3 Pages 790-792
    Published: 1981
    Released: June 02, 2006
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    The reactions of (thioacyloxy)silane (O-trimethylsilyl thioacetate and thiobenzoate) with some aldehydes (propionaldehyde, butylaldehyde, and benzaldehyde) gave S-(1-substituted alkyl) thioacetates (S-[1-(trimethylsilyl-oxy)propyl, and -butyl] thioacetates, and S-[α-(trimethylsilyloxy)benzyl] thioacetate), and the three corresponding thiobenzoates respectively. The reactions were catalyzed by 1,8-diazabicyclo[5.4.0]undec-7-ene(DBU), and also by its salt with thiobenzoic acid.
  • Yasuhiko Sawaki, Yoshiro Ogata
    1981 Volume 54 Issue 3 Pages 793-799
    Published: 1981
    Released: June 02, 2006
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    Formation of peroxycarboximidic acid (1) is not rate-determining in the reaction of nitrile with alkaline hydrogen peroxide to form amide and oxygen; the yield of amide based on H2O2 varies from 20 to 60%. When dimethyl sulfoxide (DMSO), a reactive substrate, is added, the rate is independent of [DMSO] and governed in turn by a rate-determining addition of HOO to nitrile. This reaction gives a reliable α-value of kHOO/kHO, which is 10000 for benzonitrile. A facile conversion of nitrile to amide may be achieved by the reaction in the presence of DMSO, unaccompanied by side reactions such as the epoxyamide formation from α,β-unsaturated nitrile. Kinetics and product analysis suggest that a predominant reaction is not a non-radical oxidation of H2O2 with 1 but a radical decomposition of H2O2 which is induced by the homolysis of anion of 1 (1A). No singlet oxygen could be trapped chemically. The reaction of superoxide ion, O2\ ewdot, with acetonitrile is shown to be analogous to that of HOO; the decomposition of O2\ ewdot is fast in the presence of MeCN and DMSO in benzene, affording acetamide and dimethyl sulfone.
  • Yoshio Fuchita, Kazuhisa Hidaka, Shigeki Morinaga, Katsuma Hiraki
    1981 Volume 54 Issue 3 Pages 800-804
    Published: 1981
    Released: June 02, 2006
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    cis-[PdCl2(PPh2R1)(CN–C6H4–CH3-p)] (R1=Ph or Et) reacts with nitrilimines or nitrilylides, derived from the reactions of either N-phenylarenecarbohydrazonoyl chlorides or N-(p-nitrobenzyl)arenecarboximidoyl chlorides with triethylamine, to afford novel cyclic carbene–palladium(II) complexes, viz. 1,2,4-triazol-5(4H)-ylideneor 2-imidazolin-5-ylidenepalladium(II) ones, respectively. Halogen exchange reactions of the carbene complexes with lithium bromide or sodium iodide give the corresponding dibromo- or diiodocarbene complexes, respectively. trans-[PdI2(PPh2-C6H4-CH3-p)(CN-C6H4–NO2-p)] also reacts with the nitrilimine or the nitrilylide to produce cyclic carbene–palladium(II) complexes. All the complexes prepared in this study are characterized by elemental analysis, IR and 1H-NMR.
  • Eiichi Nakamura, Koichi Hashimoto, Isao Kuwajima
    1981 Volume 54 Issue 3 Pages 805-808
    Published: 1981
    Released: June 02, 2006
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    Silylation of ketones, alcohols, alkanethiols, phenols, and carboxylic acids with alkyl trimethylsilylacetates has been described from synthetic and mechanistic points of view.
  • Yoshio Inoue, Yoshiaki Miyata
    1981 Volume 54 Issue 3 Pages 809-816
    Published: 1981
    Released: June 02, 2006
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    The molecular dynamics of the inclusion complexes of cycloamyloses with phenylalanine in aqueous solution at different pD have been studied by means of carbon-13 NMR spectroscopy. As host cycloamyloses we have chosen cyclohexaamylose, cycloheptaamylose, and cyclooctaamylose. The influences of the cavity size of cycloamyloses and of medium pD values on the molecular dynamics of inclusion complexes were studied by using the NT1η values, where T1 is the carbon-13 spin-lattice relaxation time, N the number of directly bonded proton to a given carbon, and η is the viscosity of solution. Upon complexation, the NT1η values of phenyl carbons of guest phenylalanine show larger decreases than those of other carbons, indicating that the guest forms the inclusion complexes with the host by the insertion of its phenyl ring into the host cavity even in the case of cyclooctaamylose. It was found that the strength of the dynamic coupling between host and guest depends on the cavity size and pD values of medium. The strongest coupling was observed for the cycloheptaamylose–phenylalanine system at pD 11.3, where the phenyl ring is deeply and tightly included into the cavity. The inclusion of phenyl ring is shallow and loose in the case of cyclohexaamylose and deep and loose in the case of cyclooctaamylose.
  • Mikio Watanabe, Seijin Nakamori, Hatsue Hasegawa, Kozo Shirai, Takanob ...
    1981 Volume 54 Issue 3 Pages 817-821
    Published: 1981
    Released: June 02, 2006
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    The Pummerer rearrangement reaction of 2- or 3-substituted 4-(phenylsulfinyl) butyric acids in the presence of an excess amount of acetic anhydride and a catalytic amount of p-toluenesulfonic acid in refluxing toluene for 1 h afforded 2- or 3-substituted 4-phenylthio-4-butanolide (17af). Thermolysis in pyridine of 4-phenylsulfinyl 4-butanolides, which were prepared by oxidation of 17a–f, afforded 2- or 3-substituted 2- or 3-buten-4-olides.
  • Toshihiko Migita, Mitsumasa Nakayama, Toshiro Watanuki, Mikio Suzuki, ...
    1981 Volume 54 Issue 3 Pages 822-827
    Published: 1981
    Released: June 02, 2006
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    Selectivities in halogenation of 2,3-dimethylbutane, 1-chlorobutane and substituted toluenes with N-chloro-or N-bromo derivatives of 4,4-dimethyl-2-oxazolidinone (NXDMO), 2-oxazolidinone (NXO), and succinimide (NXS) were examined. In the presence of olefin, halogenation of the substituted butane by these N-halo reagents were found to proceed involving hydrogen abstraction by the N-centered radicals, since chlorination by the N-chloro reagents and bromination by the corresponding N-bromo reagents showed the same selectivities. The relative reactivity of a t-C-H bond compared with a prim-C-H bond RSpt markedly depends on the structure of the N-radical, being 200, 70, and 11 at 80 °C toward the radicals derived from NXDMO, NXO, and NXS, respectively. Reaction constant ρ of hydrogen abstraction from the toluenes by the N-radical from NXDMO was −1.0 at 130 °C.
  • Makoto Komiyama, Hidefumi Hirai
    1981 Volume 54 Issue 3 Pages 828-831
    Published: 1981
    Released: June 02, 2006
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    A correlation between the penetration depth of the carbon atoms of 4-nitrophenolate, benzoic acid, 4-nitrophenol and 2,6-dimethyl-4-nitrophenolate in the cavity of α-cyclodextrin and the changes of their 13C-chemical shifts has been investigated. By use of this relationship and the observed changes of the 13C-chemical shifts of 3-nitrophenol on the complex formation with α-cyclodextrin, the time-averaged conformation of the α-cyclodextrin-3-nitrophenol complex is determined.
  • Nobuo Ishikawa, Hiroshi Iwakiri, Kazuya Edamura, Satoshi Kubota
    1981 Volume 54 Issue 3 Pages 832-835
    Published: 1981
    Released: June 02, 2006
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    Acylchlorination of mono-, 1,1-di-, and trifluoroethenes with carboxylic acid chlorides using AlCl3 and FeCl3 as a Lewis acid was investigated. In AlCl3-catalyzed reactions, fluorine-chlorine exchange reaction always occurred in part, while in FeCl3-catalyzed reactions Claisen-type condensation giving β-diketones was observed. Preparations of 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, and 2-chloro-1,2,2-trifluoroethyl ketones are given.
  • Taeko Izumi, Mitsugi Maemura, Kazuyoshi Endoh, Tadashi Oikawa, Satoshi ...
    1981 Volume 54 Issue 3 Pages 836-839
    Published: 1981
    Released: June 02, 2006
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    [π-(Dimethylaminomethyl)cyclopentadienyl]tetraphenylcyclobutadienecobalt(I) reacts with lithium tetrachloropalladate(II) in the presence of sodium acetate to give an ortho-palladated binuclear complex. The σ-bonded structure of the complex was confirmed by studies of the IR and 1H-NMR spectra and of the reactions with triphenylphosphine, thallium(I) acetylacetonate, and lithium aluminum deuteride. The reactions of the σ-bonded complex with carbon monoxide and olefins have been examined.
  • Seiji Shinkai, Naotoshi Nakashima, Toyoki Kunitake
    1981 Volume 54 Issue 3 Pages 840-845
    Published: 1981
    Released: June 02, 2006
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    The cleavage of amide substrates (p-nitro-N-methyltrifiuoroacetanilide and p-nitro-N-methyldichloroacetanilide) with anionic nucleophiles was studied at 30 °C in aprotic (acetonitrile and N,N-dimethylformamide) and protic(ethanol) media. Hydrogencarbonate ion acted as catalyst much more efficiently in the aprotic solvents (about 103 fold) than expected from its aqueous pKa, but in ethanol, its reactivity was close to those of simple nucleophiles (p-cyanophenolate anion and N-hydroxysuccinimide anion) that possess analogous pKa values in water. The reaction rate in the aprotic solvents was sensitive to small amounts of water. The kinetic isotope effect showed that proton transfer was involved (at least partially) in the rate-determining step. Thus, hydrogencarbonate ion behaves in aprotic media as a nucleophilic-general acid catalyst for the amide cleavage. The biochemical implication with regard to the action of biotin was discussed.
  • Hiroshi Suginome, Norio Maeda, Yuko Takahashi, Nobuyoshi Miyata
    1981 Volume 54 Issue 3 Pages 846-851
    Published: 1981
    Released: June 02, 2006
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    The photoreaction of 4,4-dimethylcholest-5-en-3-one oxime, a β,γ-unsaturated ketone oxime, has given two lactams, 4a,4a-dimethyl-3-aza-A-homocholest-5-en-4-one and 4a,4a-dimethyl-4-aza-A-homocholest-5-en-3-one resulting from photo-Beckmann rearrangement. 4,4,6-Trimethylcholest-5-en-3-one oxime behaved analogously on photolysis, yielding two lactams but accompanied by 4,6-dimethyl-4-methylene-3,4-secocholest-5-ene-3-nitrile as a minor product. In contrast, major products in the ordinary Beckmann rearrangement are nitriles resulting from the second order Beckmann rearrangement.
  • Hiroshi Suginome, Hitoshi Ono, Tadashi Masamune
    1981 Volume 54 Issue 3 Pages 852-861
    Published: 1981
    Released: June 02, 2006
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    Catalytic hydrogenation of (22S,25S)-N-acetyl-3β,23β-dihydroxyveratra-5,13(17)-dien-11-one 3-acetate over rhodium-platinum catalyst in acetic acid gave (22S,25S)-N-acetyl-3β,23β-dihydroxyveratranin-11 -one 3-acetate (2) in ca 70% yield, together with two minor products. Irradiation of 2 in benzene containing mercury(II) oxide and iodine gave 20-formyl-3β-hydroxy-12α,17β-ethyletiojervan-11-one 3-acetate (5) in 43% yield, accompanied by the 17-epimer of (22S,23R,25S)-N-acetyl-3β-hydroxy-5α-jervanin-11-one 3-acetate (4%). Aldehyde 5 was transformed into 3β-hydroxy-12α,17β-ethyletiojervane-11,20-dione 3-acetate (15) (79% yield) by photo- or coppercatalysed oxygenation of the corresponding enamine. Reduction of 15 with sodium borohydride gave 3β,20β-dihydroxy-12α,17β-ethyletiojervan-11-one 3-acetate (17) as a major product (69%), together with the 20-epimer. The hypoiodite reaction of 17 gave 18,20β-epoxy-3β-hydroxy-17β-ethyl-12α-etiojervan-11-one 3-acetate (19) in 92% yield. Hydrolysis of 19 resulted in the isomerization of the C/D ring junction to give 18,20β-epoxy-3β-hydroxy-17β-ethyletiojervan-11 -one (20), the first 18-functional C/D trans D-homo-C-norsteroid ever prepared. Wolff-Kishner reduction of 20 gave the corresponding 11-deoxo compound; its acetylation followed by oxidation yielded 18,20β-epoxy-3β-hydroxy-17β-ethyletiojervan-18-one 3-acetate. The 11-oxo function of 19 can be reduced quite easily with lithium aluminum hydride to give the corresponding 11β-ol.
  • Kiyofumi Murakami, Takayuki Sano, Tatsuya Yasunaga
    1981 Volume 54 Issue 3 Pages 862-868
    Published: 1981
    Released: June 02, 2006
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    The interaction of Bromphenol Blue (BPB) with bovine serum albumin (BSA) was studied statically, by spectrophotometry, and kinetically, by the pressure-jump method. The absorbance changes of BPB were monitored at 20 °C, pH 7.00 in 0.2 M phosphate buffer. The static measurements showed that there were two binding classes. The number of binding sites and the binding constants for each class are n1=1, K1=1.4×107 M−1 and n2=3, K2=9.5×104 M−1. Kinetically, the binding of BPB to the primary binding site of BSA proceeds via at least 4 steps. Two models are offered for the possible binding mechanism. In these models, a fast, probably diffusion controlled, second order step is followed by three first order steps. A correlation between the number of binding steps and the magnitude of the binding constant is discussed. The positive activation entropies associated with the backward reactions of the second and third steps show that these reactions proceed through disordered activation states. From the comparison of the present results to those for other ligands, it was found that the ligand is intimately involved in which activated configuration is adopted.
  • Mitsuyasu Kawakami, Hideaki Iwanaga, Shuichi Kagawa
    1981 Volume 54 Issue 3 Pages 869-872
    Published: 1981
    Released: June 02, 2006
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    Diffusion coefficients at zero concentration, D0, for hydrocarbon vapors in natural rubber have been determined, and their dependence on the size and shape (or length) of the penetrants has been reexamined. For normal hydrocarbons, D0 decreased gradually with increasing the number of carbon atoms up to 5 and then leveled off. For branched hydrocarbons, such as iso- and neo-paraffins, D0 was considerably lower than that for the corresponding normal ones. The dependence of D0 on the size and shape of penetrants could be explained by assuming that the principal resistance to diffusion is defined by the cross-sectional area at the most bulky portion of the major axis and also that an additional resistance due to the molecular length contributes for relatively lower hydrocarbons. The latter resistance was practically negligible for hydrocarbons with more than 4 carbon atoms in the major chain. The effective cross-sectional dimension could be estimated successfully in terms of the group dimension of Pauling.
  • Akira Kuboyama
    1981 Volume 54 Issue 3 Pages 873-877
    Published: 1981
    Released: June 02, 2006
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    The electronic absorption and MCD spectra and phosphorescence spectra at 77 K, in solutions, have been studied by the use of P-P-P-method calculations. The longest-wavelength S–S ππ* band, near 370 nm, is proved to consist of two ππ* bands, the 1A1 and 1B2 bands. The nπ* absorption, and phosphorescence bands in various kinds of solutions are compared in many respects with those of the o-quinones previously studied.
  • Haruto Muraishi
    1981 Volume 54 Issue 3 Pages 878-883
    Published: 1981
    Released: June 02, 2006
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    Mg(OH)2 powder packed into a basket was placed apart from solid SiO2 in an autoclave so that the SiO2 might react with the solid Mg(OH)2 in the state of soluble silica. At given temperatures of 250–360 °C, the Mg(OH)2 changed into talc(Mg3Si4O10(OH)2) through serpentine(Mg3Si2O5(OH)4): the reaction was a first-order consecutive-irreversible reaction which can be represented as:
    Mg(OH)2\overset+SiO2→ Mg3Si2O5(OH)4\overset+SiO2→ Mg3Si4O10(OH)2.
    The reaction rate of serpentine into talc as a single reaction was also first-order. The formation of serpentine was much faster than that of talc. The reaction rate depended on the silica concentration in the hydrothermal solution rather than on the reaction temperature. In the course of the reaction, the crystallite size of the Mg(OH)2 and the serpentine was hardly changed. In addition, the crystallite size of Mg(OH)2 did not affect that of the resulting serpentine. From these results, the rate-limiting step is presumed to be the formation of the crystal nuclei of the serpentine or talc.
  • Tadaaki Kakutani, Kenji Kano, Shinji Ando, Mitsugi Senda
    1981 Volume 54 Issue 3 Pages 884-890
    Published: 1981
    Released: June 02, 2006
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    The electrochemical redox reaction of flavin mononucleotide (FMN) adsorbed on a hanging mercury drop electrode was studied in a pH 6.9 phosphate buffer and a pH 4.9 acetate buffer by means of cyclic d.c. and phasese lective a.c. voltammetry. Both the oxidized and reduced forms of FMN arc strongly adsorbed on the electrode surface, and a stable adsorption layer of FMN((FMN)ad) is formed. The cyclic d.c. and a.c. voltammetric behavior of (FMN)ad is explained by equations for a two-step one-electron surface redox reaction. The formal standard redox potentials, semiquinone formation constants, and charge transfer-rate constants of the surface redox reaction of FMN at the mercury electrode were determined.
  • Hideo Ueda, Chuji Katayama, Jiro Tanaka
    1981 Volume 54 Issue 3 Pages 891-896
    Published: 1981
    Released: June 02, 2006
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    The molecular structures of tetramethyl[3.3]paracyclophadine(I) and [3.4]paracyclophadiyne(II) have been determined by X-ray analysis. Both crystals are monoclinic, with the space group of P21/c. The crystal data are: a=9.170(4), b=9.208(3), c=18.232(7) Å, β=94.0(1)°, Z=4 for (I) and a=10.938(3), b=9.173(2), c=14.988(4) Å, β=116.1(1)°, Z=4 for (II). In both molecules, consisting of benzene and diacetylene groups linked by two methylene-bridges, the diacetylene chain is bent into a bow shape. The (I) molecule has Cs symmetry, and the distances (3.019–3.256 Å) between the atoms of the diacetylene group and the benzene plane are smaller than those of [3.3]paracyclophadiyne(Aono, Sakabe, Sakabe, Katayama, and Tanaka, 1975). The methylene-bridge of [3.4]paracyclophadiyne has a disordered structure.
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