Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 54 , Issue 4
Showing 1-50 articles out of 76 articles from the selected issue
  • Toshiki Wakabayashi, Katsuko Takaizumi
    1981 Volume 54 Issue 4 Pages 951-956
    Published: 1981
    Released: June 02, 2006
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    Studies have been carried out on the hydration of quaternary phosphonium bromides, Bu4−nPhnPBr(n=0–4), in the chloroform phase by means of distribution equilibrium and 1H NMR spectroscopy, in order to clarify the difference between the alkyl- and aryl-substituted ions in ion–water interactions. The hydration constant for these bromides in the chloroform phase increases gradually from Bu4PBr to Bu2Ph2PBr, and then rapidly to BuPh3PBr and to Ph4PBr. The free energy of transfer from water to chloroform was evaluated for the non-hydrated species of the phosphonium bromides in the chloroform phase, the lowest being that for Bu2Ph2PBr. From 1H NMR spectra for water in the chloroform phase, it is concluded that the hydrated water molecule is hydrogen bonded with the anion of the onium salts. In the case of phenyl-rich cations such as BuPh3P+, Ph4P+, and Ph4As+ the water molecule occupies a site so close to the central atoms that it undergoes diamagnetic effects of phenyl groups. With phenyl-rich cations such hydration will play a certain role in their aqueous solutions.
  • Tsutomu Miyasaka, Akira Fujishima, Kenichi Honda
    1981 Volume 54 Issue 4 Pages 957-961
    Published: 1981
    Released: June 02, 2006
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    The photoelectrochemical behavior of chlorophyll a-lipid mixed monolayers coated on a platinum electrode by the Langmuir-Blodgett technique was investigated under potentiostatic conditions in an aqueous electrolyte in the absence of redox agents. Under illumination, cathodic photocurrents were observed at electrodes coated with a sufficient number of monolayers. The quantum efficiency of the photocurrent was estimated to be about 10−4, much lower than that obtainable for dye-sensitized photocurrent on semiconductor electrode. The cathodic photocurrent increased with lowering in the pH of electrolyte. The possibility of the photoreduction of water by excited triplet chlorophyll a is discussed on the basis of observed pH dependence and correlation of the redox potentials involved.
  • Setsuo Kashino, Norimitsu Sasahara, Shin-ichi Kataoka, Masao Haisa
    1981 Volume 54 Issue 4 Pages 962-966
    Published: 1981
    Released: June 02, 2006
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    The crystal structures of hexamethyleneiminium p-chlorobenzoate (1), and the monoclinic [2(m)] and orthorhombic [2(o)] forms of hexamethyleneiminium p-bromobenzoate have been determined from visually estimated Cu Kα data. The crystal data are: P21c, a=10.10(2), b=16.78(1), c=9.01(2) Å, β=118.4(2)°, Z=4 for 1; C2/c, a=25.47(2), b=7.01(1), c=16.29(1) Å, β=109.1(1)°, Z=8 for 2(m); and Pbca, a=11.55(1), b=27.40(1), c=8.57(1) Å, Z=8 for 2(o). The structures of 1, 2(m), and 2(o) were refined to R values of 0.072, 0.100, and 0.083 for 1628, 1009, and 1013 non-zero reflections, respectively. In the crystals of 1, the type of hydrogen bond and the molecular arrangement in (010) plane are the same as those in piperazinediylium terephthalate. In 2(m), two pairs of the base and acid ions related by a twofold axis are linked together by N–H···O hydrogen bonds. The crystal structure of 2(o) is very similar to that of piperidinium and pyrrolidinium p-substituted benzoates in Pbca, but there is a difference in the combination mode of the base and acid ions participating in the hydrogen bonds. In all the crystals, the hydrogen bond extending along the long axis of the acid ion is shorter than that nearly perpendicular to the axis. Hexamethyleneimine rings in 1, 2(m), and 2(o) take a similar twist-chair conformation.
  • Kazuhiro Ishida, Shuichi Kadowaki, Teijiro Yonezawa
    1981 Volume 54 Issue 4 Pages 967-970
    Published: 1981
    Released: June 02, 2006
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    Two-configuration SCF wave functions constructed with multiconfiguration SCF localized-orbitals are obtained for several molecules, cations, and anions. The weights of the valence-bond resonance-structures are obtained from the wave functions for these molecules and molecular ions. A new formula of the ionic character of a chemical bond is proposed using these weights. For these neutral molecules, the values calculated from this formula are consistent with Pauling’s scale of the ionic character. The present formula is shown to be applicable even for molecular ions.
  • Tohru Inoue, Ryoichi Tashiro, Ryosuke Shimozawa
    1981 Volume 54 Issue 4 Pages 971-974
    Published: 1981
    Released: June 02, 2006
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    Some contradictions are pointed out in the kinetic parameters of the fast relaxation in a micellar solution deduced from the previously proposed kinetic models. A modification of the previous models is proposed. The proposed model eliminates the contradictions and leads to a consistent interpretation of the experimental results.
  • Miki Niwa, Kunihiko Yagi, Yuichi Murakami
    1981 Volume 54 Issue 4 Pages 975-979
    Published: 1981
    Released: June 02, 2006
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    A magnetic resonance study was performed in order to determine the phase of iron oxide supported on Al2O3 and to measure in situ the surface conditions during the reaction. The irreversible transition of α-Fe2O3 into Fe3O4 by the reduction of the supported catalyst and the reversible transition between Fe3O4 and γ-Fe2O3 were confirmed at 280 °C. The spectrum appearing at g=2.03 and having the line width of about 1000 gauss clearly showed ferrimagnetic behavior; it could be attributed to the ferrimagnetic resonance (FMR) of Fe3O4 and/or γ-Fe2O3. Kinetic study suggested that the CO–N2O reaction took place in the oxidation-reduction mechanism. The concentration of γ-Fe2O3 was calculated from not only the kinetic equation, but also the in situ measurement of the FMR signal; these values were consistent. The γ-Fe2O3/Al2O3 had nearly the same activity as the α-Fe2O3/Al2O3, whereas the unsupported γ-Fe2O3 had a lower activity than the α-Fe2O3. Such a difference in catalytic activity was discussed in comparison with other oxidation reactions.
  • Yuriko Nitta, Fumimaro Sekine, Toshinobu Imanaka, Shiichiro Teranishi
    1981 Volume 54 Issue 4 Pages 980-984
    Published: 1981
    Released: June 02, 2006
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    Enantioselective hydrogenation of methyl acetoacetate to methyl 3-hydroxybutyrate with various unsupported nickel catalysts modified by (2R,3R)-tartaric acid was studied under mild conditions in order to elucidate the dependence of the selectivity upon the surface states of the catalysts. The catalyst with the larger crystallite size has the higher enantioselectivity, presumably because of the higher probability to obtain large ensembles of regularlyarranged nickel atoms in the catalyst surface for the modifier to adsorb strongly and regularly. The nickel boride catalyst has very low enantioselectivity, mainly due to its amorphous structure. The detrimental effect of additives (B, P, and Al in Ni–B, Ni–P, and R–Ni catalysts) was explained as the effect of their lowering the crystallinity of the catalysts.
  • Toshiyuki Hiramatsu, Toshiaki Harada, Teizo Yamaji
    1981 Volume 54 Issue 4 Pages 985-990
    Published: 1981
    Released: June 02, 2006
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    New anthracene derivatives with a –COCH– group, such as 1,5-dipropionylanthracene, 1,8-dipropionylanthracene, 1,5-di-isobutyrylanthracene, 1,8-diisobutyrylanthracene, 1,5-bis[3-(methoxycarbonyl)propionyl]anthracene, 1,8-bis[3-(methoxycarbonyl)propionyl] anthracene, 1,5-bis(cyclohexylcarbonyl) anthracene, 3,7-diisopropyl-1,5-diisobutyrylanthracene, and 5-dimethylamino-4-isobutyryl-1-methoxyanthracene (10) have been synthesized. Their direct chemiluminescences were studied by air oxidation in alkaline solutions. The properties of the chemiluminescence have been found to be influenced by not only the class of the C–H bond adjacent to the carbonyl group but also by the electronic properties of the aromatic ring system, the solvent, and the additive. 10 exhibited the longest chemiluminescence. This chemiluminescent phenomenon might be explained by a chemically initiated electron exchange luminescence (CIEEL) mechanism.
  • Nobuyuki Ito, Koichi Saito, Tadashi Kato, Tsunetake Fujiyama
    1981 Volume 54 Issue 4 Pages 991-997
    Published: 1981
    Released: June 02, 2006
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    Rayleigh scattering spectra were observed for the binary solutions of t-butyl alcohol(TBA)–water and 2-butoxyethanol (BE)–water. The observed line-widths were reduced to mutual diffusion coefficients. The observed concentration dependencies of the mutual diffusion coefficients were well explained by postulating the existence of “moving units”— a group of molecules which move together for a time much longer than the velocity autocorrelation time. The structure of the moving units which are formed in the TBA–water solution was (H2O)20TBA for XTBA\lesssim0.05, and 4(H2O)20TBA for XTBA\gtrsim0.05, where XTBA is the mole fraction of TBA. For the BE–water solution, the structure was found to be (H2O)50BE for XBE\lesssim0.02 and 3(H2O)50BE for XBE\gtrsim0.02. These results were compared with the results which had been obtained from the concentration dependencies of the mean-square concentration fluctuation values.
  • Noriaki Hirayama, Akio Takenaka, Yoshio Sasada, Ei-ichi Watanabe, Hisa ...
    1981 Volume 54 Issue 4 Pages 998-1004
    Published: 1981
    Released: June 02, 2006
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    The structure of the triclinic form of octaethylporphinium (monocation) triiodide was determined by X-ray analysis. The structure of the previously determined orthorhombic form was refined using diffractometer data. The final R values for the triclinic and the orthorhombic forms were 0.060 and 0.069, respectively. The present analysis has established the inherent structure of porphyrin monocations; three pyrrole rings are coplanar and the plane of the fourth ring is tilted from the mean plane of the other three. The magnitude of the tilt angle is 12.5° for the triclinic form and 16.1° for the orthorhombic form.
  • Harumichi Tsukada, Hirotaka Shimanouchi, Yoshio Sasada
    1981 Volume 54 Issue 4 Pages 1005-1009
    Published: 1981
    Released: June 02, 2006
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    trans-1,2-Dicyanoethylene (DCNE) reacts with substituted benzo[1,2 : 4,5]dicyclobutene (1) to give only one adduct (4), the title compound, whereas tetracyanoethylene (TCNE) gives two isomers. Crystals of 4 are triclinic; space group P\bar1, a=13.505(2), b=14.118(2), c=10.722(1) Å, α=98.87(1), β=102.36(1), γ=111.71(1)° and Z=2. The structure was solved by the direct method and was refined by the block-diagonal least-squares method to the final R factor of 0.055 for 5479 observed reflections. The absence of two cyano groups in 4 makes less steric hindrance than 3. Introducing the empirical parameters, non-bonded interaction energy was calculated for the approaching model of 1 and DCNE. The result well explains the addition of DCNE to the C(1)–C(6) position of 1.
  • Hironobu Kunieda, Stig E. Friberg
    1981 Volume 54 Issue 4 Pages 1010-1014
    Published: 1981
    Released: June 02, 2006
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    The phase equilibrium in C8H17(OCH2CH2)3OH/water/decane system was studied at 13.6, 15.8, 21.5, 26.0, and 30.0 °C. An upper critical solution point for the surfactant and oil phases, and a lower critical solution point for the surfactant and water phases were found. Strong critical opalescence was observed in the vicinity of the critical points. In a temperature range between two critical points, a three-phase region appeared due to the superposition of three miscibility gaps, i.e., 1) surfactant+water; 2) surfactant+oil, and 3) oil+water phases. The correlations between the phase equilibria and the ultralow interfacial tensions were straightforward. An ionic surfactant/cosurfactant/brine/oil system gave similar phase equilibria as the nonionic surfactant system, but the effect of temperature was the reverse.
  • Hiroyoshi Kanai, Keiji Ishii
    1981 Volume 54 Issue 4 Pages 1015-1018
    Published: 1981
    Released: June 02, 2006
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    Methyl acrylate was hydrodimerized in a methanolic solution by CoX(PPh3)3 (X=halogen) into dimethyl adipate. The in situ prepared cobalt complexes from cobalt halides, triphenylphosphine, and zinc gave higher yields of the hydrodimer in the presence of alkali halides. A mechanism is proposed which involves the protonation of Co(I)–methyl acrylate π-complex to give (2-methoxycarbonylethyl)cobalt complex, followed by a further addition of methyl acrylate.
  • Kazunori Takaoka, Roger G. Bates
    1981 Volume 54 Issue 4 Pages 1019-1024
    Published: 1981
    Released: June 02, 2006
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    The transport number of the ions, t±, of (C2H5)4NClO4, NaClO4, NaCl, KCl, and HCl in N,N-dimethylformamide(DMF)–water solvents were determined by the agar–salt bridge method. In order to compare this method, t+(HCl)’s in DMF–water media were measured by both the Hittorf method and the concentration cell method. Good agreement among these methods leads to the conclusion that t+(KCl) and t(KCl) are nearly equal in the whole range of DMF–water media. The results suggest that potentials obtained in nonaqueous polarography with the bridged SCE by correcting the bridge potential with a slow flowing type aqueous SCE are always referred to the ordinary aqueous SCE.
  • Noriaki Ikeda, Tadashi Okada, Noboru Mataga
    1981 Volume 54 Issue 4 Pages 1025-1030
    Published: 1981
    Released: June 02, 2006
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    The mechanism of the strong fluorescence quenching observed when two conjugated π-electron systems are directly connected by hydrogen bonding has been studied by means of transient absorption spectral measurements with ps as well as ns laser photolysis method and fluorescence measurement. The bimolecular rate constants of quenching of 2-naphthylamine fluorescence by pyridine and 4-cyanopyridine have been determined in various solvents. The bimolecular reaction rate of fluorescence quenching by pyridine is smaller than the diffusion controlled one in many cases and depends considerably upon the dipole moment and the ability of formation of hydrogen bonding chain of solvent. However, the quenching by 4-cyanopyridine is diffusion controlled in every solvent examined here. By means of ps laser photolysis method, the state formed by charge transfer from excited 2-naphthylamine to hydrogen bonded pyridine in the quenching process has been observed for the first time. The possibility of the hydrogen atom transfer due to the mechanism of charge transfer followed by proton transfer in hexane solution is also discussed.
  • Kazuo Tokiwano, Kiyoshi Arakawa
    1981 Volume 54 Issue 4 Pages 1031-1039
    Published: 1981
    Released: June 02, 2006
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    A molecular dynamics “experiment” has been performed for a system of 216 molecules interacting through a modified Lennard-Jones-type potential. The velocity autocorrelation functions and associated self-diffusion coefficients were computed for varying degrees of the steepness of the repulsive part in the pair potential. The dependence of these quantities upon the hardness of the core, and then the applicability of a perturbation approach to the transport theory, was elucidated. The computed self-diffusion coefficients were compared with the prediction of the Rice-Allnatt theory.
  • Isao Sanemasa, Kenji Haraguchi, Hideo Nagai
    1981 Volume 54 Issue 4 Pages 1040-1043
    Published: 1981
    Released: June 02, 2006
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    The effects of 11 salts, NaCl, NaNO3, Na2SO4, NaBr, NaSCN, NaF, NaClO4, KCl, BaCl2, (CH3)4NBr, and (C2H5)4NBr, on the solubility of elemental mercury in water have been studied at 25 °C. Salting coefficients were determined and compared with those predicted by both the McDevit-Long equation and the scaled particle theory (SPT). The McDevit-Long equation gave reasonably good predictions except for NaBr, NaClO4, and NaSCN. SPT is also applicable to prediction of the salt effect when the energy parameter of mercury determined from the Henry law constant of aqueous solubility of mercury vapor is employed. Attempts to predict the effects of tetraalkylammonium salts by SPT failed.
  • Katsuma Hiraki, Toyohiko Masumoto, Yoshio Fuchita, Yasushi Zegi
    1981 Volume 54 Issue 4 Pages 1044-1047
    Published: 1981
    Released: June 02, 2006
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    A new tertiary phosphine containing α,β-unsaturated β-amino ketone, 4-[2-(diphenylphosphino)ethylamino]-3-penten-2-one (Hdpeap), reacts with sodium tetrachloropalladate(II) in the absence or presence of sodium ethoxide to give [PdCl2(Hdpeap)2] or [PdCl(dpeap)] [dpeap ≡ 4-[2-(diphenylphosphino)ethylamino]-3-penten-2-onatoO,N,P], respectively. The latter complex reacts with terminal acetylenes in the presence of catalytic amounts of copper(I) iodide to produce alkynyl complexes, [Pd(C≡CR)(dpeap)]. Carbanions derived from active methylene compounds, and sodium dimethyldithiocarbamate also react with [PdCl(dpeap)] to afford [Pd(CHYY′)(dpeap)] and [Pd(S2CNMe2)2], respectively.
  • Ken-ichi Machida, Gin-ya Adachi, Yoshikazu Moriwaki, Jiro Shiokawa
    1981 Volume 54 Issue 4 Pages 1048-1051
    Published: 1981
    Released: June 02, 2006
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    The crystal structures of Eu2B5O9X (X=Cl and Br) were determined by the method of X-ray diffraction analysis and refined by the least-square method to give R=0.054 for 1967 observed reflections of Eu2B5O9Cl and R=0.047 for 1979 observed reflections of Eu2B5O9Br. These haloborates are isostructural and belong to the orthorhombic (pseudotetragonal) system, with the Pnn2 space group and with four formula units in a cell of those dimensions: a=11.364(3), b=11.301(3), and c=6.504(2) Å for Eu2B5O9Cl, and a=11.503(3), b=11.382(3), and c=6.484(2) Å for Eu2B5O9Br. The structure consists of a three-dimensional (B5O9) network, the B5O12 groups of three BO4 tetrahedra and two BO3 triangles being linked together with one another. The Eu and X atoms are located alternately in tunnels of the (B5O9) network extending along the c axis. Each Eu atom is surrounded by two X atoms and seven O atoms, and is isolated from the neighboring Eu atoms attributable to borate units and X atoms. This arrangement of anions around Eu atoms relates to the fact that the Eu2+-activated phosphors of alkaline earth analogs give emissions with a high quantum efficiency.
  • Ken-ichi Machida, Gin-ya Adachi, Hajime Hata, Jiro Shiokawa
    1981 Volume 54 Issue 4 Pages 1052-1055
    Published: 1981
    Released: June 02, 2006
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    The europium(II) orthoborate Eu3(BO3)2 is trigonal, space group R\bar3c, with a=9.069(1), c=12.542(2) Å and Z=6. The structure has been refined to R=0.082 for 259 observed reflections with isotropic thermal parameters. The borate contains isolated and planar triangle BO33− ions, the anions and Eu atoms being hexagonally packed along c. Each Eu atom is surrounded by 8 oxygens with Eu–O distances varying from 2.36 to 2.95 Å. The interatomic distances between Eu atoms are 3.509–4.200 Å for 8 nearest Eu neighbors and 4.831–5.450 Å for 6 second-nearest Eu neighbors. The 6 nearest Eu neighbors with the interatomic distances of 3.509 and 3.778 Å and the 4 second-nearest Eu neighbors with the Eu–O–Eu angle of 166.0° are effective for the magnetic exchange and superexchange interactions between Eu2+ ions, giving rise to ferromagnetism at low temperature.
  • Kazuhiko Nakayama, Takashi Komorita, Yoichi Shimura
    1981 Volume 54 Issue 4 Pages 1056-1062
    Published: 1981
    Released: June 02, 2006
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    Six square-planar complexes, [PdL(meso-stien)](ClO4)2 (meso-stien=meso-1,2-diphenyl-1,2-ethanediamine; L=N,N-diethylethylenediamine, N,N-dimethylethylenediamine, 2-methyl-1,2-propanediamine, N2,N2-dimethyl-2-methyl-1,2-propanediamine, N, N-dimethyl-1,3-propanediamine, and (2S)-N1,N1diethyl-1,2-propanediamine), were prepared and optically resolved (or separated in the case of the last named ligand) using diacetyl-d-tartaric anhydride as the resolving agent. Their electronic absorption and CD spectra were measured. A definite additivity has been confirmed between the configurational CD caused by the chiral configuration and the vicinal CD due to the asymmetric carbon atom in the (2S)-N1,N1-diethyl-1,2-propanediamine complex. Absolute configurations of this and the other five complexes have been assigned by examining molecular models and the CD spectra.
  • Masahiro Mikuriya, Naoyuki Torihara, Hisashi Okawa, Sigeo Kida
    1981 Volume 54 Issue 4 Pages 1063-1067
    Published: 1981
    Released: June 02, 2006
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    The crystal structure of binuclear manganese(III) complex, Mn(spa)(ac) (H2spa=3-salicylideneamino-1-propanol, ac=acetate), was determined by the single-crystal X-ray diffraction method. The crystals are triclinic, space group P\bar1, a=8.804(3), b=9.376(3), c=8.671(3) Å, α=111.24(3), β=101.34(3), γ=65.00(3)°, and Z=1. The structure was solved by the heavy atom method and refined by the block-diagonal least-squares method to an R factor of 0.034. The crystal structure consists of discrete binuclear clusters, where the two manganese atoms are bridged by two alkoxo oxygens of the spa ligands and two bidentate acetate ions. The structural detail is in conformity with the magnetic and spectral properties previously reported.
  • Emiko Ohyoshi
    1981 Volume 54 Issue 4 Pages 1068-1071
    Published: 1981
    Released: June 02, 2006
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    The formation of the mixed ligand complexes of heavy rare earth elements with α-hydroxyisobutyric acid (AHIB or HA) and nitrilotriacetic acid (NTA or H3L) was studied by electromigration. The equations expressing the zone mobility as a function of the concentrations of the two ligands were derived with or without the mixed ligand complexes, MLA. The experimental results showed that the MLA complexes were formed. The formation constants for the Tb(III), Dy(III), Ho(III), Er(III), Tm(III), Yb(III), and Lu(III) complexes were determined. The results obtained by using the two series of solutions, with varying [L3−] at a constant [A] and with varying [A] at a constant [L3−], were in good agreement. The stability trend was in an ordinary decreasing sequence of: Lu>Yb>Tm>Er>Ho>Dy>Tb.
  • Keiko Kamisawa, Keiji Matsumoto, Shun’ichiro Ooi, Reiko Saito, Y ...
    1981 Volume 54 Issue 4 Pages 1072-1076
    Published: 1981
    Released: June 02, 2006
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    The crystal structures of wine-red [Cu(1,3-chxn)2]Br2 (1), [Cu(1,3-chxn)2](NO3)2 (2), and blue-violet [CuCl(1,3-chxn)2]ClO4 (3) (1,3-chxn=cis-1,3-cyclohexanediamine) have been determined from the diffractometer data measured by the use of Mo Kα radiation. The structures were solved by the Patterson–Fourier method and refined by the least-squares method to R=0.042 (1), 0.033 (2), and 0.057 (3) for 1309, 1210, and 776 nonzero reflections respectively. The Cu atoms in 1 and 2 have a square-planar coordination by 4 N atoms, while the complex ion in 3 has a 5-coordinate square-pyramidal geometry, with the Cl atom at the apical position. The 6-membered chelate rings in 1, 2, and 3 are of the chair, flattened-chair, and envelope conformations respectively. The complex ions in 1 and 2 have virtually a C2h symmetry, the two-fold axis of which lies on the CuN4 plane. The virtual symmetry for [CuCl(1,3-chxn)2]+ is C2v, the approximate two-fold axis being coincident with the Cu–Cl bond. The cyclohexane rings (chair conformation) in 2 and 3 are roughly perpendicular to the coordination plane, but that in 1 leans toward the central Cu(II) atom. The formation of such coordinatively unsaturated Cu(II) complexes as 13 is attributable to the steric hindrance of the bulky cyclohexane ring to the axial coordination site.
  • Toshihiko Uchiyama, Kazuhiko Takagi, Keiji Matsumoto, Shun’ichir ...
    1981 Volume 54 Issue 4 Pages 1077-1084
    Published: 1981
    Released: June 02, 2006
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    trans-Dichlorobis(benzonitrile) platinum(II) reacted with twice the molar amount of thallium(I) acetylacetonate and benzoylacetonate in dichloromethane at room temperature to afford mainly N-acetyl β-ketoamine chelates, trans-[Pt{N(COMe)=C(Ph)CH=COMe(and Ph)}2] (1a and 3a). This N,O-chelate structure of 1a was determined by X-ray analysis. Reactions of cis-[PtCl2(PhCN)2] gave C-acetyl and C-benzoyl β-ketoamine chelates, cis-[Pt{NH=C(Ph)C(COMe(and Ph))=COMe}2], together with other minor products. Formation of these β-ketoamine chelates is explained by the nucleophilic reactions of the β-diketonate carbanions at the coordinated cyanide carbon atom, followed by migration of the acetyl group or the methine proton of the nucleophiles onto the imino nitrogen atom formed during these reactions. In the presence of free β-diketones, migration of the acyl group was generally suppressed; this led to high yields of C-acyl complexes especially in reactions of cis-[PtCl2(PhCN)2]. In each case, the reaction proceeded with retention of the geometrical configuration around the central metal atom. The structures of other products, including a compound obtained by acid hydrolysis of 1a, were explored and discussed, based on IR and 2H NMR data.
  • Seichi Okeya, Shun’ichiro Ooi, Keiji Matsumoto, Yukio Nakamura, ...
    1981 Volume 54 Issue 4 Pages 1085-1095
    Published: 1981
    Released: June 02, 2006
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    A number of palladium(II) and platinum(II) bis-chelates have been prepared which contain one kind of symmetric or unsymmetric β-diketonate anions, or involve two different β-diketonate anions. Existence of the cis and trans isomers in solution of the binary chelates of unsymmetric β-diketones was confirmed by 1H and 13C NMR spectroscopy. Geometrical isomerization of the palladium(II) complexes to attain equilibrium in solution is fast, while the platinum(II) complexes are quite inert. The mixed-ligand chelates are stable in solution, showing no sign of disproportionation. The isomeric pairs of bis(1-phenyl-1,3-butanedionato)palladium(II), bis(2,4-hexanedionato)palladium(II), and bis(1,1,1-trifluoro-2,4-pentanedionato)platinum(II) were isolated, and molecular structure of the cis isomer of the first complex was determined by X-ray analysis.
  • Tasuku Ito, Koshiro Toriumi, Haruko Ito
    1981 Volume 54 Issue 4 Pages 1096-1100
    Published: 1981
    Released: June 02, 2006
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    A complex dihydrate formed with nickel(II) bromide and the title macrocyclic ligand (memo-Me6[14]aneN4) crystallizes in triclinic space group P\bar1 and in orthorhombic space group Pcab. The crystal and molecular structures of the two crystal modifications have been determined by single crystal X-ray diffraction. In each compound, the nickel(II) is surrounded by a square-planar array of nitrogen atoms, giving low-spin complexes. In both compounds, water of crystallization and bromide ions are located above the hydrogen atoms of N–H groups and form hydrogen-bonded chelate rings of the type Ni–N–H···Br···H–O···H–N. The N–H groups adjacent to the single methyl carbon and the geminal dimethyl carbon interact with bromide ion and water, respectively, in the P\bar1 form, whereas vice versa in the Pcab form. Water molecules in the present crystals and those in the previously reported crystal structure of [Ni(meso-Me6[14]aneN4)]Cl2·2H2O are involved in the same type of specific hydrogen-bonds. Because of the specific hydrogen-bonding effects, the presence of water prevents coordination of not only water itself but also halide ions, yielding thereby low-spin four coordinate complexes.
  • Masato Nanasawa, Hiroyoshi Kamogawa
    1981 Volume 54 Issue 4 Pages 1101-1104
    Published: 1981
    Released: June 02, 2006
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    The title effect has been investigated with the imidazolyl group either externally added or intramolecularly combined. N-Retinylidenebutylamine was protonated with imidazole derivatives under neutral conditions and was absorbed at longer wavelengths compared with carboxylic acids. The absorption peak with the imidazolyl group intramolecularly combined was highly affected by the structure, protonated Nα-retinylidene-L-histidine octadecylamide having an absorption maximum at 494 nm caused by the inductive effect and the polar imidazolyl group.
  • Toshimasa Ishida, Satomi Shimizu, Masatoshi Inoue, Kunihiro Kitamura, ...
    1981 Volume 54 Issue 4 Pages 1105-1107
    Published: 1981
    Released: June 02, 2006
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    The crystal structure of N-(thioacetyl)tryptamine, a radioprotective agent, has been determined by the X-ray method. The crystal is monoclinic, space, group P21/c with the unit cell dimensions: a=23.761(5), b=5.553(1), c=8.889(2) Å, and β=94.04(4)°. The structure was solved by the direct method and succesive Fourier syntheses, and refined by the block-diagonal least-squares method to give a final R-value of 0.072. In the crystal, the molecules are held together with van der Waals contacts between the nonpolar groups of adjacent molecules, and an inter-molecular hydrogen bond between the sulfur and nitrogen atoms of the side chain (N–H···S=3.322 Å). The folded conformation observed in this compound could be related to the protection of DNA against irradiation.
  • Kenichi Yoshikawa, Noriyuki Kumazawa, Hiroshi Terada, Motoharu Ju-ichi
    1981 Volume 54 Issue 4 Pages 1108-1111
    Published: 1981
    Released: June 02, 2006
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    The steric and electronic structures of the most potent uncoupler of oxidative phosphorylation known, SF 6847, and its derivatives were studied. 1H and 13C NMR measurements showed that the malononitrile moiety is not planar with the benzene ring and that its intramolecular motional freedom is reduced on acid dissociation of the phenolic proton. The activation energies of the tumbling motion of the malononitrile moiety in the anionic forms of SF 6847 and its derivatives were also determined from their 1H NMR measured at various temperatures. The CNDO/2 and ab initio MO calculations of the model compounds of SF 6847 showed that the planar form is quite unstable and that the malononitrile moiety is twisted considerably relative to the benzene ring. The effect of the dynamic structure on the acidity of SF 6847 was discussed based on the above results.
  • Kenichi Somekawa, Ryusuke Imai, Ryuichi Furukido, Sanetada Kumamoto
    1981 Volume 54 Issue 4 Pages 1112-1116
    Published: 1981
    Released: June 02, 2006
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    Sensitized photoirradiations of 2-pyridones with tetrachloroethylene or trichloroethylene gave chlorinated 3-azabicyclo[4.2.0]oct-4-en-2-ones (1) and 2-azabicyclo[4.2.0]oct-4-en-3-ones (2 and 3), 7,7,8-trichloro-2-methyl-2-azabicyclo[2.2.2]oct-5-en-3-one (4), and other products. The reaction with 1,1-dichloroethylene, though, gave only 7,7-dichloro-3-azabicyclo[4.2.0]oct-4-en-2-one. 1, 2, 3, and 4 were reduced by zinc to give 7,8-dichloromethyl-3-azabicyclo[4.2.0]octa-4,7-dien-2-one, 2-azabicyclo[4.2.0]octa-4,7-dien-3-ones (7) and 6-chloro-2-methyl-2-azabicyclo[2.2.2]octa-5,7-dien-3-one respectively. Then, 7 thermally gave valence isomers, 7-azabicyclo[4.2.0]octa-2,4-dien-8-ones, which were β-lactams.
  • Yoshinobu Inouye, Chikara Fukaya, Hiroshi Kakisawa
    1981 Volume 54 Issue 4 Pages 1117-1125
    Published: 1981
    Released: June 02, 2006
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    1,6-Diketone, available in eight steps from homocamphorquinone, was converted into 1,5,5,11,11-pentamethyltricyclo[6.2.1.02,6]undecan-7-one by treatment with potassium t-butoxide and then lithium dimethylcuprate, while α,α-dimethyl-γ-valerolactone, prepared in five steps from homocamphor, was converted into 1,5,5,11,11-pentamethyltricyclo[6.2.1.02,6]undec-2-en-4-one by treatment with diphosphorus pentoxide–methanesulfonic acid.
  • Osamu Kikuchi, Hiroshi Kubota, Keizo Suzuki
    1981 Volume 54 Issue 4 Pages 1126-1131
    Published: 1981
    Released: June 02, 2006
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    The photochemical electrocyclic reaction paths of s-cis-acrylaldehyde to oxetene were examined on the basis of the potential surfaces obtained by the MINDO/3 CI calculation, and compared with those of the corresponding conjugated hydrocarbon system. The strong S0-S2 interaction, which appears in the disrotatory mode of the cyclization of butadiene, was not observed in the acrylaldehyde–oxetene system. There appears to be a step-by-step path, in which the π→π* induced rotation of the methylene group is followed by the ring-closing step. The zwitterion in which the positive charge is localized on the terminal carbon atom is involved in this step. Since the σ lone-pair electrons of the oxygen atom play a key role in the ring-closing step, this path is characteristic of the hetero-atom conjugated system and cannot be deduced by analogy or by a simple extension of the concepts established for the photoreactions of all-hydrocarbon conjugated systems. The possible decay paths from acrylaldehyde in the excited states were also discussed.
  • Chung-gi Shin, Yasuchika Yonezawa, Masatoshi Takahashi, Juji Yoshimura
    1981 Volume 54 Issue 4 Pages 1132-1136
    Published: 1981
    Released: June 02, 2006
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    The direct coupling between N-protected α-dehydroamino acid (1) and N-free α-dehydroamino acid ester (2) by the acid-chloride method was carried out to give several dehydrodehydrodipeptides (7). Furthermore, the two kinds of dehydrodipeptides with a hydroxyl group, obtained by the coupling of 1 with a serine or threonine ester, and that of N-protected serine or threonine with 2, followed by mesylation and subsequent base-catalyzed β-elimination gave a number of 7 substances in good yields. The configurational structures of 7 obtained by both direct condensation and elimination were found to have (Z,Z)-geometry.
  • Chung-gi Shin, Yoshiaki Sato, Hisao Ohmatsu, Juji Yoshimura
    1981 Volume 54 Issue 4 Pages 1137-1142
    Published: 1981
    Released: June 02, 2006
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    The facile conversion of α-dehydroamino acid into α-alkoxy-α-amino acid and its cyclic dipeptide is described. The reaction of t-butyl 2-acetylamino-2-alkenoate or 1-benzyl-3-ethylidene-2,5-piperazinedione with alcohol, water, or acetic acid in the presence of NBS or NGS, followed by reduction with 10% Pd–C, gives t-butyl 2-alkoxy-, 2-hydroxy-, and 2-acetoxy-2-(acetylamino)alkanoates, and 3-alkoxy-3-ethyl-2,5-piperazinedione respectively. All the new compounds were characterized by spectroscopic analysis.
  • Norio Kunieda, Akira Suzuki, Masayoshi Kinoshita
    1981 Volume 54 Issue 4 Pages 1143-1150
    Published: 1981
    Released: June 02, 2006
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    The reaction of α-lithio aryl methyl sulfoxides with a limited amount of chiral carboxylates (R2–CO–O–R*) was found to be an enantiomer-differentiating reaction, affording the corresponding optically active β-keto sulfoxides (3), together with optically active aryl methyl sulfoxides which have the opposite configuration. The optical purity and the predominant configuration of 3 obtained were assigned by means of a combination of polarimetric analysis and NMR. The degree of enantioselectivity of this reaction was affected by the nature of the ester moiety R2, indicating an increase in optical yields, from 1.3%, where R2 was ethyl (3b), to 70.3%, where R2 was t-butyl (3f). The stereochemical course of the reaction has been discussed by considering a six-membered cyclic transition state. Furthermore, the repeated recrystallizations of several β-keto sulfoxides thus obtained, such as (−)-3e, (−)-3f, (−)-3g, and (−)-3p, were found to give the corresponding highly optically pure β-keto sulfoxides.
  • Shozo Yanagida, Yukihiro Noji, Mitsuo Okahara
    1981 Volume 54 Issue 4 Pages 1151-1158
    Published: 1981
    Released: June 02, 2006
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    Perfluoro-2-methyl-2-pentene (PMP) reacts with carboxylic acids, alcohols, and 2-pyridone, giving Michaeltype addition products, 1,1,1,3,4,4,5,5,5-nonafluoro-2-trifluoromethyl-3-acyloxypentane, 1,1,1,3,4,4,5,5,5-nonafluoro-2-trifluoromethyl-3-alkoxypentane, 1,1,1,3,4,4,5,5,5-nonafluoro-2-trifluoromethyl-3 (2-pyridyloxy)pentane, respectively, in good yields. In the presence of bases, carboxylic acids give acid fluorides, 1,1,1,4,4,5,5,5-octafluoro-2-trifluoromethyl-3-pentanone, and 1,1,1,4,4,5,5,5-octafluoro-2-trifluoromethyl-3-acyloxy-2-pentene (4), the yields changing with base, solvent, phase-transfer catalyst, and their combination. In the presence of triethylamine, fluorination occurs exclusively, producing acid fluorides in good yields. Alcohols and 2-pyridone are converted into alkyl fluorides and 2-fluoropyridine, respectively, with use of triethylamine as a base with an aprotic solvent. The reactions of PMP with 4-pyridone and 6-chloro-2-ethyl-5-methyl-4(3H)-pyrimidone were also examined. The fluorination reactions were rationalized by preferential replacement of the vinylic fluorine of PMP and a good leaving function of the perfluoro enol group of the intermediates such as 4.
  • Masaaki Yoshida, Makoto Kobayashi, Masahiro Minabe, Kazuo Suzuki
    1981 Volume 54 Issue 4 Pages 1159-1162
    Published: 1981
    Released: June 02, 2006
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    The sulfonation of 4H-cyclopenta[def]phenanthrene gave 1-sulfonic acid accompanied by formation of 2-, 3-, and 8-analogues. The reaction of 8,9-dihydro derivative with sulfuric acid in acetic anhydride yielded exclusively the 2-acid. Also, 4H-cyclopenta[def] phenanthren-4-one afforded the 8-acid as the main product, and 1- and 2-isomers as minor products. The formation of the keto 2-sulfonic acid would be controlled thermodynamically and that of the 8-isomer is controlled kinetically.
  • Yoshihito Watanabe, Tatsuo Numata, Takashi Iyanagi, Shigeru Oae
    1981 Volume 54 Issue 4 Pages 1163-1170
    Published: 1981
    Released: June 02, 2006
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    The oxidation of alkyl sulfides, sulfoxides, and sulfones was examined with either rabbit liver microsomes or a reconstituted system containing purified cytochrome P-450, S-dealkylation being found to take place more readily with alkyl sulfides bearing a higher acidic α-hydrogen. Similar results were obtained in the oxidation of alkyl sulfides by hydroxyl radical. Both S-dealkylation and S-oxygenation products are presumed to be formed via the cation radical intermediate.
  • Tadashi Yoshida, Yosuke Maekawa, Tetsuo Higuchi, Eiji Kubota, Yasuhiro ...
    1981 Volume 54 Issue 4 Pages 1171-1175
    Published: 1981
    Released: June 02, 2006
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    Field-ionization (FI) and field-desorption (FD) mass-spectroscopic techniques have been applied to the analysis of ring-type fractions of coal-derived oil, obtained by liquid chromatography. These techniques produce only the molecular ion and its isotopic signals, free from fragment ions, of a molecule, consequently the exact molecularweight-distribution profiles of chromatographic fractions. The peak intensities are reproducible within a variation coefficient (σ/\barx) of about 5–8% on repeated runs. The number-average molecular weights (\barMn) of the ring-type fractions, as calculated from the peak intensities, are close to those obtained by means of a vapor-pressure osmometer (VPO). These techniques, on the whole, give reliable mass spectra of coal-derived oil, although the isotope-ion ratios are overestimated compared to the theoretical natural abundances. The group-type analysis of the ring-type fractions has been made on the basis of their mass spectra, and the skeletal structures corresponding to each mass z series have been proposed.
  • Akira Yabe
    1981 Volume 54 Issue 4 Pages 1176-1182
    Published: 1981
    Released: June 02, 2006
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    Transient absorbing in the 400–450 nm range was observed in the photolysis of 1,4-diacetoxy-2,3-diazidonaphthalene in rigid matrices at 77 K. The transient was assigned as α,α′-diacetoxv-α,α′-dicyano-o-xylylene by comparison with the low-temperature photolysis of the other precursors, 1,2-diacetoxy-1,2-dicyano-1,2-dihydrobenzocyclobutenes. The three o-xylylene stereoisomers showed differences in the longest-wavelength absorption maxima. Continued irradiation of the o-xylylenes converted them to 2-acetoxy-2-methyl[1,3]dioxolo[4,5-c]isoquinoline-5-carbonitrile as the result of the reaction of a cyano group with the o-xylylene system and the migration of an acetoxyl group. The rate of formation of the isoquinoline in rigid matrices depends on the viscosity of glassy solvents and the configuration of the intermediate o-xylylenes. The room-temperature photolysis of the diazide gave 2,3-diacetamido-1,4-naphthoquinone as the main product and compounds via the o-xylylene as minor products. A mechanism involving two competitive reactions is discussed.
  • Seizi Kozuka, Tetsuji Higashino
    1981 Volume 54 Issue 4 Pages 1183-1185
    Published: 1981
    Released: June 02, 2006
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    Kinetic studies have been conducted for the reactions of ethoxytrimethylsilane with benzenesulfinyl chloride and aryloxytrimethylsilane with methanesulfinyl chloride. Both the reactions were found to obey second order rate equation. A clear negative ρ value was observed for the reaction of aryloxytrimethylsilane. The solvent effects suggested that both the two reactions were quite similar in their mechanisms. Nucleophilic addition of silyloxygen atom to sulfinyl group has been suggested for these two reactions.
  • Hitomi Suzuki, Mitsuyuki Hashihama, Tadashi Mishina
    1981 Volume 54 Issue 4 Pages 1186-1190
    Published: 1981
    Released: June 02, 2006
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    When treated with concentrated nitric acid in dichloromethane at room temperature, the title compounds undergo an exclusive attack on the methyl group at the most crowded site, giving 6-acyl-2,3,4,5-tetramethylbenzyl nitrates, and 2,6-diacyl-3,4,5-trimethylbenzyl nitrates and/or (2,6-diacyl-3,4,5-trimethylphenyl)nitromethanes respectively, as the major products. While the predominant mode of the side-chain substitution reactions is nitrooxylation for acylpentamethylbenzenes and 1,3-dipivaloyl-2,4,5,6-tetramethylbenzene, it shifts to nitration for 1,3-bis(trihalogenoacetyl)-2,4,5,6-tetramethylbenzenes. Nitrodeacylation is seen to some extent for pivaloylbenzenes, but not for trihalogenoacetylbenzenes. The exclusive attack on the methyl group at the most hindered position can be explained by a sequence involving the attachment of a nitronium ion at the site meta to the acyl group, followed by a proton release from the resulting arenium ion to form a nitromethylenecyclohexadiene intermediate, which is then transformed into the benzylic compounds via a benzyl cation/nitrite anion pair.
  • Yukinori Nagao, Takahisa Misono
    1981 Volume 54 Issue 4 Pages 1191-1194
    Published: 1981
    Released: June 02, 2006
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    The condensations of 3,4 : 9,10-perylenetetracarboxylic dianhydride with alkylamines (isobutyl-, pentyl-, hexyl-, and octylamines) were spectroscopically determined. Under all of the reaction conditions employed, N-alkyl-3,4 : 9,10-perylenetetracarboxylic monoanhydride monoimide (2ad) (alkyl=a; isobutyl, b; pentyl, c; hexyl, d; octyl) were obtained. As the reaction proceeded, the yield of 2ad increased at an initial stage but decreased gradually after reaching a maximum. This maximum yield of 2ad was: 2a; 85–88%, 2b; 85–89%, 2c; 78–84%, 2d; 79–85%. The kinetics of the reaction were also examined.
  • Kazuo Irie, Ken-ichi Watanabe
    1981 Volume 54 Issue 4 Pages 1195-1198
    Published: 1981
    Released: June 02, 2006
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    The rate of the condensation of benzaldehyde with excess acetophenone catalyzed by Co(II) acetate-2,2′-bipyridine complex was obtained by GLC analysis. The rate increased in proportion as the amount of the complex catalyst. 2,2′-Bipyridine ligand in the Co(II) complex enhanced the catalytic activity remarkably, though the ligand itself had no activity. When the molar ratio of Co(II): bpy was 1 : 1 or 1 : 2, the highest activity was observed. The activation energy of the complex (1 : 1) catalyzed reaction was calculated as 13.7 kcal/mol. The catalysis of the complex behaved like a base catalyst. Briefly, the relation of the complex catalyzed aldol condensations with the enzymatic reaction of Class II aldolase is also described.
  • Teruo Mori, Michinori Oki
    1981 Volume 54 Issue 4 Pages 1199-1202
    Published: 1981
    Released: June 02, 2006
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    The title compounds were prepared to see the effect of an 8-methyl group on the populations and the barriers to rotation of rotamers. As expected, the substituent destablized the syn conformation to a considerable extent, although the extent appeared to be a little less than that of a 2-t-butylphenyl group. Atropisomers of 1-methyl-9-(8-methyl-1-naphthyl)fluorene were isolated. The barriers to rotation were discussed with reference to related compounds.
  • Teiichiro Ogawa, Naoki Yamami, Masaharu Tsuji, Yukio Nishimura
    1981 Volume 54 Issue 4 Pages 1203-1207
    Published: 1981
    Released: June 02, 2006
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    The emission spectra of benzene, toluene, ethylbenzene, xylenes, trimethylbenzenes, cymene, and naphthalene were investigated under controlled electron-impact excitation. These aromatic hydrocarbons showed a characteristic band in the 250–400 nm region and several bands of such excited fragment species as H and CH. The characteristic bands are similar to those of fluorescence spectra obtained by optical excitation and, thus, were assigned to fluorescence emissions of the parent molecules. The intensity of the fluorescence emission of benzene decreased at higher electron energies, and fragment emissions became dominant above 100 eV. However, its vibrational structure did not change for electron energies of 5–60 eV. This indicates that cascade processes from high-lying states are negligible for benzene. The fluorescence emission of naphthalene shifted to a shorter wavelength for low electron energies. Together with a theoretical estimation based on the Born approximation, cascade effects from higher excited states (S2 and S3) are found to be the major source of the fluorescence emission of naphthalene.
  • Yukio Nagahira, Kazunori Matsuki, Hideo Fukutome
    1981 Volume 54 Issue 4 Pages 1208-1216
    Published: 1981
    Released: June 02, 2006
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    The electronic absorption spectra of fatty acid multilayers with bivalent metal ions were studied in the vacuum ultraviolet (VUV) to ultraviolet (UV) energy region below 8 eV; they are due to transitions in the carboxylic acid and metal carboxylate moieties. Infrared (IR) absorptions due to the C–O stretching vibration in the carboxylate moiety are also studied. Stearic acid multilayers without metal ions are shown to form hydrogen-bonded dimers. The spectra of multilayers with metal ions show a marked dependence on the subphase pH which is different for different kinds of adsorbed metal ions. Their VUV spectra are conspicuously dependent on the kind of metal ions adsorbed. All the multilayers with alkaline earth metals, metals of the 2B group, transition metals, Cu, and Pb have at least two bands in the VUV region, 7.3–6.3 eV. The polarization spectra of the Ba stearate multilayer suggest that the two transitions may be the intramolecular π-π* and n* transitions in the carboxylate anion moiety. The multilayers with Cu and Pb have another band in the UV region. The spectra of the UV bands of the Pb and Cu stearate mono-, bi-, and multilayers were studied. In the Pb stearate layers, the positions of the UV bands in the bi- and multilayers are the same, but those in the monolayers are at considerably shorter wavelengths. The positions of the UV band in the Cu stearate mono-, bi-, and multilayers are successively red shifted. The polarization spectra of the UV bands of the mono- and bilayers showed that they are charge-transfer bands between the Pb or Cu ion and the coordinated carboxylate moiety.
  • Yukio Nagahira, Kazunori Matsuki, Hideo Fukutome
    1981 Volume 54 Issue 4 Pages 1217-1221
    Published: 1981
    Released: June 02, 2006
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    The electronic absorption spectra of fatty acid multilayers were measured in the vacuum ultraviolet region with an energy below 10 eV. From the chain length dependence of the spectra, the strong absorption (above 8 eV) was assigned to the σ-σ* transitions in the alkane chain moiety, and the weaker one (below 8 eV), to the transitions in the car boxy lie acid and metal car boxy late moieties. The polarized spectra of the Ba stearate multilayer showed that the band near 8.8 eV was polarized perpendicularly to the alkane chain. The spectra of the stearic acid multilayer without metal ions and the multilayer of the Zn stearate showed that their alkane chains were titled against the normal of the layer plane.
  • Ken-ichi Kowari, Ko-ichi Sugawara, Shin Sato, Shigeru Nagaset
    1981 Volume 54 Issue 4 Pages 1222-1226
    Published: 1981
    Released: June 02, 2006
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    The apparent decay rates of hydrogen and deuterium atoms in the reactions with acetylene-d0 and -d2 in helium in the pressure range from 100 to 800 Torr (1 Torr=133.3 Pa) have been measured by the pulse radiolysisLyman-α absorption method at 300±2 K. The helium pressure dependence of the rate constants was well interpreted in terms of the RRKM theory including a tunneling effect, using the geometry and force constants of the activated complex and vinyl radical estimated by the ab initio calculation. (S. Nagase and C. W. Kern, J. Am. Chem. Soc., 101, 2544 (1979).)
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