Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 50 , Issue 11
Showing 1-50 articles out of 68 articles from the selected issue
  • Yoshiya Kera, Keiji Kuwata
    1977 Volume 50 Issue 11 Pages 2831-2836
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    Two types of ESR spectra were found in the highly purified V2O5 crystal under conditions of SO2 oxidation. The shapes and the intensities of the spectra were investigated in detail in the temperature range from 470 to 656 °C under various mixing ratios of SO2 to O2. Below ca. 600 °C a sharp and asymmetric spectrum existed stably, while above that temperature it was replaced by a spectrum with an hfs of 29 lines, the intensities of which always were very weak. The low-temperature-type spectrum was reasonably assigned to the VOSO4 phase, and the high-temperature-type, to an oxygen defect surrounded equivalently by four vanadium ions in the V2O5 phase. The interchange between the two spectra near 600 °C occurred reversibly and was related favorably to the following process in the surface layer of the V2O5 crystal: 2VOSO4=V2O5+SO3+SO2. The change in the working states of a pure V2O5 crystal according to the conditions of SO2 oxidation was discussed.
  • Masatoshi Chikazawa, Takafumi Kanazawa
    1977 Volume 50 Issue 11 Pages 2837-2840
    Published: 1977
    Released: April 19, 2006
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    The amounts of methanol adsorbed on (100) planes of the crystals of six alkali halides (LiCl, NaCl, NaBr, KCl, KBr, and KI) and the isosteric heats of their adsorption were measured. For the chloride samples, the order of magnitude of the adsorption heats at a coverage of θ=0.5 was found to be LiCl>NaCl>KCl, while the order for the bromide samples was NaBr>KBr. The monolayer capacities estimated from the adsorption isotherms for KCl and NaBr were in accord with the values calculated by assuming that one methanol molecule is adsorbed on one surface anion of the crystal. In the cases of the NaCl and LiCl salts, whose lattice spacings are smaller than that of NaBr, the methanol molecule was adsorbed on the surface anion with a ratio below 1 : 1. On the other hand, for the KBr and KI samples, whose lattice spacings are larger than that of KCl, alcohol was adsorbed on the surface anion in a ratio above 1 : 1. These phenomena are reasonably interpreted in terms of a relationship between the cross-sectional area of a methanol molecule and the lattice spacing of the salt concerned. An adsorptive mechanism deduced from the isosteric heat curves was compatible with the above explanation.
  • Yoshiya Kera
    1977 Volume 50 Issue 11 Pages 2841-2846
    Published: 1977
    Released: April 19, 2006
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    By the use of highly concentrated 18O-carbon dioxide, both the rate of the isotopic exchange of CO2 and the surface oxygen of a powderd V2O5 catalyst and that of the isotopic equilibration of CO2 on the surface were determined simultaneously in the temperature range from 330 to 450 °C. The rate of the isotopic exchange on the thin-plate crystallines, in which the (010) plane of V2O5 crystal was mainly exposed, was also determined. The equilibration rate was 30–40 times faster than the exchange rate. The exchange process on the thin-plate crystallines was found to be extremely rapid, although such a phenomenon has never been found on the powdered catalyst. Based on these results, the relationship of the reaction steps of the isotopic exchange and the isotopic equilibration with those on the triangular scheme of CO-oxidation, previously proposed, was discussed in detail. A small cycle of alternate reduction-oxidation on the top of the surface, especially on the (010) plane, was conclusively confirmed.
  • Tadao Kenjo, Seishi Yajima
    1977 Volume 50 Issue 11 Pages 2847-2850
    Published: 1977
    Released: April 19, 2006
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    The ternary oxides, (La,Pr)2CuO4, (Gd,Tb)2CuO4, (La,Tb)2CuO4, (La,Ca)2CuO4 and (La,Ba)2CuO4, were prepared and their semiconducting properties were investigated. When the mean ionic radius of Ln3+ (\barr) is increased, the (La,Pr)2CuO4 compounds transform from semiconductors to metals at a critical \barr value of 1.05 Å. The metal-semiconductor transition which accompanies the shrinkage of the a axis, is explained as being due to the π-bond formation of the Cu–O bond. Compounds in the composition range from La1.3Tb0.7. CuO4 to La1.4Tb0.64CuO4 are peculiar to the (La,Tb)2CuO4 compounds. The crystal structure is the same as that of Ln2CuO4, but it is different from Ln2CuO4 as regards the c/a ratio and resistivity. The doping of 20 mol% CaO or 10 mol% BaO into La2CuO4 lowers the resistivity to tenth of that of La2CuO4.
  • Shizuo Fujiwara, Kozo Nagashima, Hiroshi Morita, Yasushi Kanaoka
    1977 Volume 50 Issue 11 Pages 2851-2853
    Published: 1977
    Released: April 19, 2006
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    A certain volume of a solution, (20–30 Å)3 per unit of solute entity, designated the “molecular space,” is assigned as the necessary volume for the free motion of the solute. By the use of ESR, the actual size of the molecular space has been determined for the cupric ion and 2,2,5,5-tetramethyl-3-carbamoylpyrollidin-1-oxyl. It is pointed out that the concentrations of the important solutions in nature, such as sea water or human serum, may correspond to the moleuclar space of ions.
  • Koichiro Miyajima, Hiromitsu Yoshida, Masayuki Nakagaki
    1977 Volume 50 Issue 11 Pages 2854-2857
    Published: 1977
    Released: April 19, 2006
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    Guanidinium halides (bromide and chloride) form crystalline complexes with symmetrical tetraalkylammonium bromides (tetraethyl-, tetrapropyl-, and tetrabutylammonium bromides and tetrabutylammonium chloride) in aqueous solutions at room temperature. These complexes were analyzed and found to be either binary complexes of two kinds of salts or ternary complexes with water as a third component. Each complex showed complicated peaks in the DSC measurements, which indicated the phase transition in the solid state. The solubility of each salt in ternary systems was measured, and phase diagrams were constructed for some of the ternary systems. A mutual salting- in effect was observed in all the ternary systems, and this effect was discussed in terms of complex formation and the structual change of water.
  • Kazuyuki Akasaka, Atsuko Yamada, Hiroyuki Hatano
    1977 Volume 50 Issue 11 Pages 2858-2862
    Published: 1977
    Released: April 19, 2006
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    Phosphorus-31 nuclear spin-lattice relaxation times and nuclear Overhauser enhancement upon nonselective proton saturation were measured on polyriboadenylic acid, polyribocytidylic acid, and polyribouridylic acid. A method is described to separate dipolar contribution from the contribution of chemical shift anisotropy for the phosphorus relaxation by the combined use of T1 and NOE data. Chemical shift anisotropies (δ⁄⁄−δ) of phosphorus in these polynucleotides in solution are estimated to be in the range 120–165 ppm. The molecular motion of the phosphorus moiety becomes faster in the order, poly(A)<poly(C)<poly(U), the thermal activation processes being characterized by single activation energies, i.e., 5.1, 5.3–6.0, and 7.2–8.1 kcal/mol for poly(U), poly(C), and poly(A), respectively.
  • Yuji Ohashi, Yoshio Sasada
    1977 Volume 50 Issue 11 Pages 2863-2869
    Published: 1977
    Released: April 19, 2006
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    The structure of (R)-1-(methoxycarbonyl)ethyl(R)(+)-α-methylbenzylaminebis(dimethylglyoximato)cobalt(III) has been determined by X-ray analysis. The crystal is monoclinic, the space group P21 Z=2 with a=7.899(5), b=16.397(2), c=9.054(7) Å, and β=90.98(7)°. The structure was deduced by the heavy atom method and refined by the block-diagonal least-squares method to a final R value of 0.048 for 2146 observed reflections. The bis(dimethylglyoximato) cobalt moiety is twisted around its long axis, owing to the steric repulsion from the (R)-1-(methoxycarbonyl)ethyl group and the optically active amine. It is proposed that this twist is one of the factors inducing the asymmetry in the hydrogenation catalyzed by the complex of bis(dimethylglyoximato)cobalt and the active amine. At the step of Co–C bond cleavage the reaction proceeds mainly through inversion of the configuration.
  • Keiichi Ohno, Keijiro Taga, Hiromu Murata
    1977 Volume 50 Issue 11 Pages 2870-2876
    Published: 1977
    Released: April 19, 2006
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    The infrared and Raman spectra have been measured for methylvinylsilane, CH2=CHSiH2(–D2)CH3, and allylsilane, CH2=CHCH2SiH3(–D3). The fundamental vibrations have been assigned, and the normal coordinate treatment for possible molecular forms has been carried out. For methylvinylsilane, the cis and skew forms coexist in the gaseous and liquid states, while only the former persists in the solid state. In the liquid state the cis form is more stable by 0.66±0.05 kcal/mol than the skew form. For allylsilane, the form near the skew form predominantly exists in the gaseous, liquid, and solid states.
  • Toyoko Imae, Shoichi Ikeda
    1977 Volume 50 Issue 11 Pages 2877-2880
    Published: 1977
    Released: April 19, 2006
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    The interaction of Acridine Orange with poly(S-carboxymethyl-L-cysteine) has been investigated by observing the solubility behavior, absorption spectra, and circular dichroism of the mixture. When the dye is added to aqueous solution of the polymer, the mixture is homogeneous at higher pH, but precipitation takes place at lower pH; the threshold pH ranges from 3.5 to 6, depending on the mixing ratio. For [P]/[D] 1 or less, the mixture is again homogeneous at very low pH between 4 and 2, when no salt is added. Various type of circular dichroism are induced for the homogeneous solutions, which are characteristic of the bound dye species on the polymer and the structure of dye–polymer complex. The binding of dye with the polymer is mainly caused by electrostatic effect, and the solubility of the mixture is interpreted by considering the ionization of polymer and the binding of dye to the polymer.
  • Masashi Tanaka
    1977 Volume 50 Issue 11 Pages 2881-2884
    Published: 1977
    Released: April 19, 2006
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    The polarized reflection spectra were measured on crystals of tetracyanoethylene and its charge-transfer complexes, and the absolute intensity of the absorption parallel to the crystalline axes has been obtained by the Kramers-Kronig transformation. The charge-transfer degree and the stabilization energy in the ground state were estimated for each complex by analyzing the charge-transfer bands in the crystalline state. In the TCNE–hexamethylbenzene(HMB), acenaphthene, and dibenzofuran complexes, the charge-transfer degrees are 9.05, 12.3, and 4.95% respectively in the ground state.
  • Motomichi Inoue, Hiroyoshi Kuramoto, Daiyu Nakamura
    1977 Volume 50 Issue 11 Pages 2885-2887
    Published: 1977
    Released: April 19, 2006
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    The powder PMR spectra of [TMPD]+(ClO4) were recorded in the temperature range 110–300 K. The spectra observed above 140 K consist of two widely separated simple absorption curves of intensity ratio approximately equal to 3 : 1. Spin densities on the carbon and nitrogen atoms of the cation radical were evaluated from the observed field shift ascribable to the Fermi contact interaction. The spin density distribution of the radical ion changes at the transition temperature of 189 K.
  • Takao Yasuda, Yasushi Kai, Noritake Yasuoka, Nobutami Kasai
    1977 Volume 50 Issue 11 Pages 2888-2891
    Published: 1977
    Released: April 19, 2006
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    The X-ray molecular structure of the addition product of trans-HPd(PEt3)2(C≡CPh) with dimethyl acetylene-dicarboxylate has been determined to be [trans-{(MeO2C)HC=C(CO2Me)}Pd(PEt3)2(C≡CPh)]. The crystal belongs to the monoclinic system, space group P21/c, with eight formula units in a cell with dimensions of a=17.844(3), b=9.476(3), c=36.061(4) Å, β=98.18(1)°. Two independent molecules have similar structures except for the conformation of the phenylethynyl groups and one of the triethylphosphine groups. The 1,2-bis(methoxycarbonyl)vinyl and phenylethynyl groups are σ-bonded to the palladium atom. No significant difference is observed between the Pd–C(sp)[2.04(2) and 2.03(2) Å] and Pd–C(sp2)[2.05(2) and 2.06(2) Å] bond lengths. The environment of the palladium atom is approximately square-planar: Pd–P=2.321(5), 2.312(5), and 2.305(5), 2.311(5) Å.
  • Naomichi Iso, Haruo Mizuno, Takahide Saito, Noriko Nitta, Katsuaki Yos ...
    1977 Volume 50 Issue 11 Pages 2892-2895
    Published: 1977
    Released: April 19, 2006
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    The self-association of phycocyanin in a buffer of pH 6.8 with an ionic strength of 0.1 has been studied by sedimentation equilibrium measurements in the temperature range from 5.2 to 25 °C. The self-association of this system increases with a decrease in the temperature. A quantitative evaluation of the experimental data for this system indicates that the type of the association reaction is not a simple mechanism such as a monomer\ ightleftharpoonsn-mer, but the discrete monomer\ ightleftharpoonstrimer\ ightleftharpoonstetramer mechanism is probable. Several thermodynamic quantities, such as the Gibbs free energy change, ΔG°, the enthalpy change, ΔH°, and the entropy change, ΔS°, accompanying the self-association reaction were computed on the basis of the equilibrium constants. From the results, it is considered that the association process is similar to the ordinary crystallization, and that the formation of a tetramer proceeds at a higher concentration than that in which the trimerization reaction is completed.
  • Setsuko Tatematsu, Kozo Kuchitsu
    1977 Volume 50 Issue 11 Pages 2896-2898
    Published: 1977
    Released: April 19, 2006
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    Emission spectra of the CN violet band system (B2Σ-X2Σ, Δυ=0) produced in the photodissociation of HCN and DCN by Lyman-α radiation (121.6 nm) were observed with resolution of about 0.2 nm and with sample pressures of 0.01–1.5 Torr. The spectral features of the two were similar, but the main peaks (υ′=0–4) from DCN appeared more sharply than the corresponding peaks from HCN. The relative vibrational populations and the effective rotational temperatures were estimated by a band-envelope analysis. No indication of vibrational population inversion was observed. The CN(B2Σ) radical produced from DCN is likely to have slightly higher vibrational (0.31±0.08 eV) measured from the zero-point energy) and rotational energies (0.15±0.02 eV) than that from HCN (0.23±0.08 and 0.11±0.02 eV, respectively).
  • Hiroshi Otokozawa, Shigehiro Inomata, Naohiko Mikami, Mitsuo Ito
    1977 Volume 50 Issue 11 Pages 2899-2901
    Published: 1977
    Released: April 19, 2006
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    The two-photon excitation spectrum of phenanthrene crystal was measured and compared with the corresponding usual one-photon absorption spectrum. It was found that the two-photon spectrum consists of a one-photon like system and a system characteristic of a two-photon process. The vibronic couplings in phenanthrene were discussed on the basis of the observed results.
  • Yonezo Maeda, Shunji Shite, Yoshimasa Takashima, Yuzo Nishida
    1977 Volume 50 Issue 11 Pages 2902-2906
    Published: 1977
    Released: April 19, 2006
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    Iron(II) complexes with the Schiff bases of 6-methyl-2-pyridinecarbaldehyde and 2-quinolinecarbaldehyde, and with α,α′-diimine were prepared. The M\ddotossbauer spectra and magnetic susceptibilities of the complexes, Fe(cbi)2(NCS)2·2/3CHCl3, Fe(tbi)2(NCS)2·CHCl3, Fe(mpmea)2(ClO4)2, and Fe(mepma)3(ClO4)2, were studied in the range of 80–298 K. It was found that these complexes show a 5T2-1A1 spin transition in the solid state.
  • Nobuo Suzuki, Koichi Saitoh
    1977 Volume 50 Issue 11 Pages 2907-2910
    Published: 1977
    Released: April 19, 2006
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    Chelate compounds of acetylacetone (2,4-pentanedione) with metal ions (Al(III), Cr(III), Fe(III), Co(III), and Be(II)) were passed through a chromatograph in columns packed with a cross-linked poly(vinyl acetate) gel (Merckogel OR-2000). Various organic solvents (chloroform, benzene, toluene, 1,4-dioxane, ethyl acetate, butyl acetate, acetone, ethyl methyl ketone, and methanol) were used as the eluents. The distribution coefficient, Kav, for each chelate in a given column system was measured to within 0.7% of the relative standard deviation. The Kav values of a chelate were dependent on the solvent used. With most of the solvents, the Kav values of the metal(III)-chelates were close together and smaller than the Kav value of the Be(II)-chelate. The effective molar volume, Veff, of the chelates thus determined, using calibration charts prepared on the basis of elution data for normal alkanes, depended strongly on the solvent used. With all the solvents except chloroform, the Feff values of each chelate were smaller than the literature value of the molar volume for that chelate.
  • Toshihiro Fujii
    1977 Volume 50 Issue 11 Pages 2911-2912
    Published: 1977
    Released: April 19, 2006
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    A simple, sensitive and practical method for the halogenated organic compound analysis of tap water is reported. A pentane extraction procedure using a ten fold increase in concentration by volume (without further concentration) followed by mass fragmentography of GC-MS was used. As little as 0.05 ppb concentration of each compound was detectable. Five simple halogenated organic compounds, including CCl4 and CHBr3 whose concentrations are relatively small, were determined for tap water in Japan.
  • Toshiaki Mitsugashira, Hajimu Yamana, Shin Suzuki
    1977 Volume 50 Issue 11 Pages 2913-2916
    Published: 1977
    Released: April 19, 2006
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    The separation and purification of 227Ac, 227Th, 223Ra, and 223Fr were studied by the solvent extraction method using HDEHP (bis(2-ethylhexyl)phosphoric acid) as an extractant. The mutual separation of Ac, Th, and Ra was achieved, and new milking processes for 223Fr and 228Ac are presented.
  • Toshio Yao, Tamotsu Wasa, Soichiro Musha
    1977 Volume 50 Issue 11 Pages 2917-2920
    Published: 1977
    Released: April 19, 2006
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    Adenine, adenosine, guanine, and guanosine were voltammetrically oxidized in a glassy carbon electrode in aqueous solutions, but at different potentials. In general, the nucleosides were oxidized at more positive potentials than their bases. The bases and their nucleosides were strongly adsorbed on the surface of the glassy carbon electrode at the pH values around neutrality, so that the concentration vs. anodic peak current curves were not linear. The adsorption on the electrode was very dependent on the pH, and at pH values below 4 good linear relationships were observed between the anodic peak current and the concentration. The differences between the peak potentials of each of the purine bases and their nucleosides were most pronounced at pH 2–4. Consequently, it was possible to determine simultaneously both in mixtures of the purine bases and their nucleosides by using Britton-Robinson buffer as a supporting electrolyte in the pH range of 2–4. The proposed method is simple and rapid, since no prior treatment or separation procedure is required.
  • Kunio Shimizu
    1977 Volume 50 Issue 11 Pages 2921-2926
    Published: 1977
    Released: April 19, 2006
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    When [RuIII(Hedta)(H2O)] was reduced at mercury electrode in sodium formate–formic acid solutions, the reduced species gradually became polarographically inactive. The final product of the deactivation reaction was isolated and identified as Na2[RuII(edta)(CO)]. The kinetics follows the second-order rate equation, −dc1dt=kobsdc1c2, where c1=[[RuII(Hedta)(H2O)]]+[[RuII(edta)(H2O)]2−] and c2=[HCOO]+[HCOOH]. The kobsd value was found to be expressed by k [H+]/(KA+[H+]), where KA (=3.28×10−4 mol dm−3) and KR (=6.92×10−4 mol dm−3) are the acid-dissociation constants of formic acid and [RuII(Hedta)(H2O)], respectively, with k=1.01×10−5 s−1 at 25 °C (ionic strength=0.5 mol dm−3). Several possible mechanisms for the reaction were discussed. Probably the reaction proceeds through the formation of an intermediate involving one formate anion followed by dehydration and rearrangement.
  • Akitoshi Komura, Mutsuo Hayashi, Hiroto Imanaga
    1977 Volume 50 Issue 11 Pages 2927-2931
    Published: 1977
    Released: April 19, 2006
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    The hydrolysis of VO2+ was investigated in 0.1 M LiClO4 by potentiometric, conductometric and turbidimetric measurements. The following values of the equilibrium constants were obtained: β11=[VOOH+] [H+]⁄[VO2+]=9.0×10−6 M (M=mol dm−3); β22=[(VO)2(OH)22+][H+]2⁄[VO2+]2=1.9×10−7 M. The solubility product of VO(OH)2 given by Kspl=[VO2+][OH]2 was found to be 6.6×10−23 M3 from the pH values at which precipitation occurs. Only one species with a stoichiometric ratio VO/OH=2.5 is present in basic solutions in the pH range 9–12. The solubility product of VO(OH)2 given by Ksp2=[H+][(VO)2(OH)5] is logKsp2=−11.1. A less soluble salt Na(VO)2(OH)5 or NaHV2O5 was isolated from strongly basic solutions. Measurements of Na+ concentration at which the solid phase first appears give logKsp3=−3.74 as its solubility product, Ksp3=[Na+][(VO)2(OH)5].
  • Kiyoshi Kuribayashi, Toshiyuki Sata
    1977 Volume 50 Issue 11 Pages 2932-2934
    Published: 1977
    Released: April 19, 2006
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    The processes of the solid state reaction of Y2O3 with WO3 were studied for samples mixed in the molar ratios of Y2O3 : WO3=1 : 3, 1 : 1, 7 : 4, 5 : 2, and 3 : 1. It was found that all the reactions except Y2O3 : WO3= 5 : 2 from the powders of both Y2O3 and WO3 in air proceeded according to the following order step reactions: Y2O3·3WO3→Y2O3·WO3→7Y2O3·4WO3→5Y2O3·2WO3 and 5Y2O3·2WO3→3Y2O3·WO3, with temperatures rising from 600 to 1300 °C and with an unknown compound, X, always first formed below 700 °C. In a reaction couple in contact with both Y2O3 and WO3 pellets, WO3 components preferentially diffused to the Y2O3 side to form Y2O3·3WO3 (orthorhombic form) on the boundary between them at 1000 °C.
  • Masayasu Iida, Hideo Yamatera
    1977 Volume 50 Issue 11 Pages 2935-2939
    Published: 1977
    Released: April 19, 2006
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    The rate of the base hydrolysis of pentaamminechlorocobalt(III) ions was measured in the presence of multivalent anions at a constant ionic strength. The results were analyzed in view of the SN1 C.B. mechanism considering the formation of ion-pairs. The ion-pairing has the effect of suppressing the acid dissociation of the complex or the formation of its conjugate base, which acts as the intermediate of the reaction. This effect out-weighs the adverse effect of the probable acceleration of the rate-determining step of the base hydrolysis. The association constants obtained for [CoCl(NH3)5]2+·SO42− and [CoCl(NH3)5]2+·P3O93− were 40±5, and 82±5, respectively (I=0.1, 25°C).
  • Hiroaki Tagawa, Takeo Fujino, Jun Tateno
    1977 Volume 50 Issue 11 Pages 2940-2944
    Published: 1977
    Released: April 19, 2006
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    The formation and nonstoichiometry of strontium uranates, especially those with the Sr/U atom ratio around unity, were examined by means of thermogravimetry and X-ray diffraction. The reaction of SrCO3 with U3O8 in air, where Sr/U=1, produced the stoichiometric β-SrUO4, which had an orthorhombic structure. The reactions in vacuum and in hydrogen yielded the products of the composition SrUO3.563 and SrUO3.175, respectively. On the other hand, the reduction of β-SrUO4 in vacuum and in hydrogen gave SrUO3.48 and SrUO3.65, respectively. Stoichiometric SrUO3 was prepared by the reaction of SrO with UO2. The reduction product of β-SrUO4, SrUC4−x, was oxidized in air below 500 °C to α-SrUO4 which was rhombohedral. During the phase transition to β-SrUO4, α-SrUO4 exhibited anomalous behavior; that is, α-SrUO4 was first reduced and then reoxidized to nearly the initial composition with the formation of β-SrUO4. Of the uranates with Sr/U\ eweq1, the formations of SrU4O13, SrU2O7, and Sr2UO5 were examined; the single phase SrU2O7 was not obtained. Thermograms for their reduction, followed by the oxidation of the resultants, suggest the existence of the compounds SrU4O11 and SrU2O6.0−6.6. No uranates containing only U(IV) were obtained by hydrogen reduction of the uranates containing U(VI) formed in air at high temperatures.
  • Yasukazu Ohkatsu, Tetsuo Osa
    1977 Volume 50 Issue 11 Pages 2945-2949
    Published: 1977
    Released: April 19, 2006
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    The effects of the kind of metal of metal porphyrins and the substituent of the phenyl group of porphynato plane were discussed, using them as catalysts in the autoxidation of aldehydes. The effect of the solvent and the additive on the above-mentioned catalytic activity of the porphyrins was put into order by means of their pKa(BH+) and pKa(BH+) values; the increased pKa(BH+), namely, the electron-donating power of solvents, seemed to lead to their strong coordination, followed by the initiation of the coordination of oxygen. On the other hand, the oxygen which had been activated on the porphyrins was estimated to react with or be stabilized by a solvent with a low pKa(H+); it could not initiate the autoxidation with ease.
  • Teijiro Miyata, Akihisa Sakumoto, Masamitsu Washino
    1977 Volume 50 Issue 11 Pages 2950-2955
    Published: 1977
    Released: April 19, 2006
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    The addition reaction induced by Co-60 gamma-rays proceeded without any detectable induction period under homogeneous conditions in the presence of sodium 1-dodecanesulfonate. The consumption rate of 1-dodecene was equal to that of sodium hydrogensulfite and proportional to the square roots of the hydrogensulfite-ion and 1-dodecene concentrations. The g-value of 1-dodecene consumption was 860 at the concentrations of 0.260 mol/l of sodium hydrogensulfite, 0.0966 mol/l of 1-dodecene, and 0.11 mol/l of sodium 1-dodecanesulfonate at the dose rate of 2.70×1015 eV/g·s and the dose of 1.62×1018 eV/g. The apparent rate constant was 2.6×10−4 s−1 under these reaction conditions. The reaction of CH3(CH2)9CHCH2SO3 with the sulfite radical ion was proposed as the termination step of the reaction.
  • Katsuhiro Kawashiro, Hideyuki Yoshida, Shiro Morimoto
    1977 Volume 50 Issue 11 Pages 2956-2960
    Published: 1977
    Released: April 19, 2006
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    N-o-Nitrophenylsulfenylamino acid amides of glycine, alanine (DL and L), leucine (DL and L), methionine (DL), phenylalanine (DL and L), and proline (L) were dehydrated in POCl3-pyridine. The N-protected α-amino-nitriles obtained were treated with anhydrous HCl affording the corresponding α-aminonitrile hydrochlorides. The optical purity of the L-α-aminonitriles was well retained.
  • Michio Kondo
    1977 Volume 50 Issue 11 Pages 2961-2964
    Published: 1977
    Released: April 19, 2006
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    The 1H NMR spectra of 3-(alkylamino)crotonamides indicate that these substances exist in solution as a mixture of the geometric isomers, cis and trans, in which the chelated cis form is predominant. Unsubstituted 3-aminocrotonamide appears to exist in the cis form only, and N,N-disubstituted derivatives in the trans form. In the case of 3-(alkylamino)crotonamide it is found that the cis-trans equilibrium is solvent dependent and that the apparent rate of interconversion between the isomers is very slow in chloroform-d, fast in dimethyl-d6 sulfoxide, and intermediate in acetone-d6 and methanol-d4. It seems that the cis-trans equilibrium is almost independent of both temperature and concentration, and that the replacement of the olefinic H by D proceeds through enamine\ ightleftharpoonsimine tautomerization.
  • Tsutomu Nonaka, Tetsuro Ota, Toshio Fuchigami
    1977 Volume 50 Issue 11 Pages 2965-2968
    Published: 1977
    Released: April 19, 2006
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    The mechanism of electrolytic reduction of 1-pyridylalkanol to the corresponding substituted-alkyl pyridine was examined by electrolyzing several optically-active 1-pyridylalkanols in an aqueous sulfuric acid solution in the vicinity of a mercury cathode. The alkyl pyridine from 1-(2-pyridyl)alkanol showed optical rotation, while that from 1-(4-pyridyl)alkanol was almost racemized.
  • Suketaka Ito, Yumo Tanaka, Akikazu Kakehi, Hirotaka Miyazawa
    1977 Volume 50 Issue 11 Pages 2969-2972
    Published: 1977
    Released: April 19, 2006
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    4-Alkyl or aryl-3,5-diphenyl-4H-1,2,4-triazoles, 3-phenyl-1,2,4-triazolo[4,3-a]pyridine, and -pyrimidine are obtained by the title reactions. The reaction may proceed via the nucleophilic attack of amidine or imidate on the imidoyl carbon of hydrazonoyl chloride and the subsequent intramolecular cyclization of the intermediate formed in the initial step, with the removal of the amino or alkoxyl and phenylsulfonyl groups.
  • Akio Takuwa
    1977 Volume 50 Issue 11 Pages 2973-2981
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    Photochemical reactions of 1,2-naphthoquinone and the substituted derivatives with a variety of aldehydes in the liquid phase have been investigated. The reaction with saturated aliphatic aldehydes gives a mixture of 3-acyl-1,2-naphthalenediol and 1,2-naphthalenediol monoacyl esters. On the other hand, the irradiation of the benzene solution of a 1,2-naphthoquinone derivative and an aromatic aldehyde gives, in general, 1,2-naphthalenediol monoaroyl esters, together with small amounts of other products. Unlike saturated aliphatic aldehydes, α, β-unsaturated aldehydes; i.e., propenal, 2-butenal, trans-2-hexenal, 1-cyclopentenecarbaldehyde, and 1-cyclo-hexenecarbaldehyde, behave similary to the aromatic aldehydes in the photochemical reaction, giving only 1,2-naphthalenediol monoesters. However, 10-undecenal, 3-phenylpropanal, cyclopentanecarbaldehyde, cyclohexanecarbaldehyde, and 3-cyclohexenecarbaldehyde give mixtures of 3-acyl-1,2-naphthalenediols and 1,2-naphthalenediol monoacyl esters similar to those from saturated aliphatic aldehydes. The origin of these significant differences is discussed.
  • Sadao Arai, Mitsuhiko Hida, Takamichi Yamagishi, Satoshi Ototake
    1977 Volume 50 Issue 11 Pages 2982-2985
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    An induction period was present in the Ullmann condensation reactions of 1-bromoanthraquinone(AQBr) with 2-aminoethanol(AE) in the presence of CuBr or CuI in aprotic solvents under a nitrogen atmosphere, while there was no induction period in the reaction systems of 1-iodoanthraquinone(AQI)–AE–CuBr, AQI–AE–CuI, and AQBr–AE–[Cu(CH3CN)4]ClO4. In the condensation system with a copper(I) catalyst, the Cu(I) species was oxidized to the Cu(II) species by means of an electron transfer from Cu(I) to haloanthraquinone as the reaction proceeded. By adding copper(II) bromide, the induction period vanished in the reaction system of AQBr–AE–CuBr. The copper(II) species increased the catalytic activity of the copper(I) species. The formation of the copper(II) species was responsible for the presence of an induction period and played an important role in the Ullmann condensation reaction of haloanthraquinones with amines in the presence of copper(I) salt as a catalyst.
  • Mikio Nakamura, Nobuo Nakamura, Michinori Oki
    1977 Volume 50 Issue 11 Pages 2986-2990
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    A series of 9-(2-alkylphenyl)fluorene derivatives are prepared and their internal rotation about the C9–Car bond is examined. Those which have a methyl, an ethyl, or an isopropyl group in 2′ position exist as a mixture of sp and ap forms, showing coalescence phenomena in the NMR spectra at high temperatures. The barriers to rotation of these compounds are obtained by the usual DNMR method. 9-(2-t-Butylphenyl)fluorene, in contrast, is found to exsist exclusively as an sp form and thus the barrier to rotation must be determined by measuring the rates of conversion from the unstable ap form which is successfully obtained by the protonation of the corresponding lithium fluorenide at low temperatures. The barriers to rotation of the compounds are alike except for the t-butyl compound. The difference is explained in terms of the conformation of the alkyl group in the ground and the transition state for rotation. The 13C NMR data also exhibit a large steric interaction between the alkyl group and the fluorene ring.
  • Hisao Ochi, Tadashi Miyasaka, Kiichi Arakawa
    1977 Volume 50 Issue 11 Pages 2991-2994
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    Acetylation of 5-hydroxy-4-(2-hydroxyethyl)-3-methylpyrazole (1) produced five acetyl derivatives: 4-(2-acetoxyethyl)-5-hydroxy-3-methylpyrazole (2), 4-(2-acetoxyethyl)-2-acetyl-5-hydroxy-3-methylpyrazole (3), 4-(2-acetoxyethyl)-1-acetyl-5-hydroxy-3-methylpyrazole (4), 5-acetoxy-4-(2-acetoxyethyl)-2-acetyl-3-methylpyrazole (5), and 1-acetyl-5-hydroxy-4-(2-hydroxyethyl)-3-methylpyrazole (6). The partial hydrolysis of 3 and 5 in aq acetic acid gave the monoacetate (2). The triacetate (5) afforded 3 by heating in a mixture of pyridine and meththanol. Migration of the acetyl group from the N1-position to the C5-O- and to the side chain-O-position is suggested. It is also suggested that the triacetate (5) may be effective for acetylation of amines.
  • Akihiko Ueno, Jun-ichi Anzai, Tetsuo Osa, Yoshinori Kadoma
    1977 Volume 50 Issue 11 Pages 2995-2999
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    Copolymers of γ-benzyl-L-glutamate with m- and p-phenylazobenzyl-L-aspartates were prepared for investigating the effect of side-chain photoisomerization on their conformations. A study was made of the circular dichroism associated with the n,π* transition of the amide group, as well as the extrinsic bands associated with the azo chromophore. The intensity of the 222-nm amide band seems unaffected by the interaction with the side-chain chromophore. The circular dichroism spectra before irradiation indicate that poly[β-(m-phenylazobenzyl)-L-aspartate] (mPALA) adopts a left-handed α-helical form and the other copolymers a right-handed form in 1,2-dichloroethane. After irradiation, remarkable changes of the 222-nm band were observed for the meta copolymer with 89.3% azo residues and mPALA. The increased absolute ellipticity for the former indicates that photoisomerization enhances the helicity of the polymer. Decrease in ellipticity for the latter indicates that photoisomerization induces significant instability of the left-handed α-helical conformation. In the course of subsequent relaxation of mPALA, an abrupt change in the CD spectra was found above 50% of cis followed by a gradual change with decreasing cis%.
  • Fumio Toda, Yozo Todo
    1977 Volume 50 Issue 11 Pages 3000-3001
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The photocyclization of the title compound afforded 14-hydroxy-4b-phenylbenz[c]indeno[2,1-a]fluoren-13-(4bH)-one, which is easily isomerized to 4b,13b-dihydro-4b-phenylbenz[c]indeno[2,1-a]fluorene-13,14-dione. The hydrogenation of both compounds gave anti-4b,8b,13a,13b-tetrahydro-4b-phenylbenz[c]indeno[2,1-a]fluorene-13,14-dione.
  • Keizo Naya, Noboru Nogi, Yasuo Makiyama, Hideo Takashina, Takashi Imag ...
    1977 Volume 50 Issue 11 Pages 3002-3006
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The dye-sensitized oxygenation of furanofukinin, and furanoeremophilane, in methanol gave, quantitatively, crystalline mixtures of two isomeric hydroperoxides each consisting of a pair of 8α-methoxy-12β-hydroperoxy and 8β-methoxy-12α-hydroperoxy derivatives respectively. The hydroperoxides were readily transformed to the corresponding lactones with acetic anhydride-pyridine through dehydration. The stereochemistry of the hydroperoxides and the corresponding lactones has been elucidated by spectral and chemical methods according to a previously outlined generalization. Further, furanofukinin, furanoeremophilane, and 8β-hydroxyeremophilenolide, have been synthesized from petasalbin, fukinone, and an epimeric mixture of 8α- and 8β-methoxy lactones, respectively.
  • Hideharu Ishihara, Shigeyuki Sato, Yoshio Hirabayashi
    1977 Volume 50 Issue 11 Pages 3007-3009
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    Diacyl selenides were synthesized in good yields by the deselenization of diacyl diselenides, which have conveniently been prepared from acyl chlorides and sodium hydroselenide. The reaction of dibenzoyl selenide with piperidine at 0 °C formed a fairly stable piperidinium salt. The methanolysis of distearoyl selenide gave selenostearic acid as an unstable intermediate.
  • Hiroshi Suginome, Norihisa Yonekura, Terutoshi Mizuguchi, Tadashi Masa ...
    1977 Volume 50 Issue 11 Pages 3010-3013
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The Photolysis of 5α-androstane-3α, 17β-diol 3-acetate 17-nitrite (1) in benzene with monochromatic light (372±4 nm) afforded two rearranged products, 17a-aza-D-homo-5α-androstane-3α,17a-diol-17-one 3-acetate (2) and the C-13 epimer (8). This result confirmed that the cyclization of the nitroso aldehyde intermediate (C) to the two products 2 and 8 proceeds without the involvement of excited species of the nitroso aldehyde intermediate C. This conclusion differs from that obtained for bornyl and isobornyl nitrites by Kabasakalian and Townley. The results of photolysis in carbon tetrachloride are also compared with that in benzene. The photolysis of the nitrite 1 in an EPA matrix at 77 K showed that essentially no β-cleavage of the 17β-oxyl radical takes place at the temperature of liquid nitrogen.
  • Takeshi Nakai, Nabil M. Hassan, Nobuo Ishikawa
    1977 Volume 50 Issue 11 Pages 3014-3017
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The reaction of hexafluoropropene(HFP) with 2-aminobenzamide afforded 2-(1,2,2,2-tetrafluoroethyl)-4(3H)-quinazolinone (4) and N-(2-cyanophenyl)-2,3,3,3-tetrafluoropropionamide (5) in ca.1 : 1 ratio, which is essentially independent of the reaction temperatures ranging from room temperature to 100 °C. The formation of the two products is explained in terms of the competitive cyclization of the imidoyl fluoride intermediate, the N-6 and O-6 ring closures ultimately yielding 4 and 5, respectively. In contrast to the HFP reaction, 2-(trifluoromethyl)pentafluoropropene (OFIB) and 2-aminobenzamide gave only the O-6 cyclized product, N-(2-cyanophenyl)-2-trifluoromethyl-3,3,3-trifluoropropionamide. The difference in reactivity between HFP and OFIB is discussed.
  • Hiroshi Nakanishi, Osamu Yamamoto
    1977 Volume 50 Issue 11 Pages 3018-3020
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    In order to obtain information about the slow rotation of methyl groups, the 1H NMR spectra of 9-t-butylethenoanthracene and 9-t-butyltriptycene derivatives were measured at very low temperatures. It was found that the signals of the two methyls of the t-butyl group in these compounds show a considerable line broadening at low temperatures, and it was made clear that the rotation of the methyl groups in these compounds is strongly restricted.
  • Toshizumi Tanabe, Kiyoshi Yamauchi, Masayoshi Kinoshita
    1977 Volume 50 Issue 11 Pages 3021-3025
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    Uracil, thymine, cytosine, adenine, and guanine were alkylated by triethyl phosphate in a homogeneous aqueous phase at 60–80 °C, giving the corresponding ethyl derivatives in considerable yields. The reactivity order on the ethylating site in each base was found to be as follows; uracil, thymine, and cytosine: N-1>N-3; adenine: N-9≈N-3>N-7, N-1; guanine: N-1>N-7>N-3, N-9.
  • Masakatsu Matsumoto, Satoshi Dobashi, Kiyosi Kondo
    1977 Volume 50 Issue 11 Pages 3026-3028
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The sensitized photooxygenation of benzofuran, 2-methylbenzofuran, and six 2-vinylbenzofurans was investigated. Benzofuran and 2-methylbenzofuran were stable toward singlet oxygen. On the other hand, the vinylbenzofurans were easily photooxygenated to give the 1,4-endoperoxides. The 1,4-cycloaddition of singlet oxygen to the 2-benzofurans was confirmed to proceed with stereospecificity.
  • Akio Yasuhara, Keiichiro Fuwa
    1977 Volume 50 Issue 11 Pages 3029-3032
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    Many aliphatic hydrocarbons, nitrogen-containing compounds, and other substances were isolated from neutral or alkaline liquid swine manure by steam distillation and column chromatography, and identified by means of gas chromatography-mass spectrometry. Aliphatic hydrocarbons have an oily odor, and nitrogen-containing substances, particularly indole, skatole, and o-aminoacetophenone, have a strong malodor. Sulfur-containing substances which have a strong malodor have been detected in a trace quantity.
  • Shozo Yamaguchi, Kuninobu Kabuto
    1977 Volume 50 Issue 11 Pages 3033-3038
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    In the enantioselective reduction of ω-substituted alkyl phenyl ketones, PhCO(CH2)nY, with lithium tri-l-menthoxyaluminum hydride, the effect of the functional groups, Y(NR2, OMe, and SMe) on the stereoselectivity was examined in comparison with that of the alkyl group. Of the functional groups tested, the MeO group is more effective in enhancing the stereoselectivity than the NMe2 or SMe group except in the case of n=1. The optical yields are also affected by the number of the methylene group (n) in the substrates. These results strongly suggest that the coordination of the Y group with the reducing reagent is one of the essential factors in the stereoselectivity. The absolute configurations of the resulting alcohols are correlated with the relative magnitudes of the lanthanideinduced shifts(LIS) of their (+)-MTPA esters.
  • Hideo Matsushima, Kozo Kitaura, Yasuki Mori
    1977 Volume 50 Issue 11 Pages 3039-3042
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    3′-Episeldomycin 5 (7) was synthesized from seldomycin 5. Reaction of hexa-N-ethoxycarbonylseldomycin 5 (2) with o-nitrobenzenesulfonyl chloride gave penta-N-ethoxycarbonylseldomycin 5-2′,3′-epicyclic carbamate (3) in one step. Hexa-N-ethoxycarbonyl-3′-O-tosylseldomycin 5 or hexa-N-ethoxycarbonyl-3′-O-mesylseldomycin 5, prepared from 2, was also converted into 3 by being heated in weakly basic solvents such as N,N-dimethylformamide or pyridine. Compound 3 was hydrolyzed to give 7. Structure of 7 was confirmed by PMR, CMR, MS, and Δ[M] values. Compound 7 was found to be active against resistant bacteria which carry 3′-O-phosphorylating enzymes. Δ[M] values for vicinal amino groups were shortly discussed.
  • Etsuo Kokufuta, Shinji Iwai
    1977 Volume 50 Issue 11 Pages 3043-3044
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The colloid titration of the maleic acid–methyl vinyl ether (MA–MVE) copolymer with trimethylammonium glycol chitosan iodide (MGCH) was carried out at various pH values. The mechanism of the formation of the polyion complex between the MA–MVE copolymer and the MGCH ions was discussed.
  • Yusuke Yamamoto
    1977 Volume 50 Issue 11 Pages 3045-3046
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    High resolution 2E→4A2 phosphorescence spectra of [Cr(NH3)6][Co(CN)6] and [Cr(NH3)6][CdCl5] were measured. The 0–0 bands split into two components separated by 3.7 and 3.4 cm−1 for [Cr(NH3)6][Co(CN)6] and [Cr(NH3)6][CdCl5], respectively. The same spacings were also resolved in the ν8 bands. The splitting in both cases is assigned as that of the 2E phosphorescent electronic level.
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