Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 46 , Issue 4
Showing 1-50 articles out of 66 articles from the selected issue
  • Akio Furusaki, Nobuyuki Hamanaka, Takeshi Matsumoto
    1973 Volume 46 Issue 4 Pages 1021-1026
    Published: 1973
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The conformation of d,l-1,1,4aα-trimethyl-2α-hydroxy-8α-acetoxy-1,2,3,4,4α,5,6,7,8,9-decahydrophenanthrene has been studied by means of X-ray methods. The crystals are triclinic, with two molecules in a unit cell with the dimensions of a=11.463, b=11.509, c=7.430 Å, α=84°42′, β=102°47′, and γ=115°40′. The space group is P\bar1. The intensity data were collected on an automatic four-circle diffractometer with CuKα radiation. The structure was solved by the symbolic-addition method, and was refined by the block-diagonal-matrix leastsquares method with anisotropic temperature factors for all the non-hydrogen atoms. From a difference Fourier map, all the 28 hydrogen atoms were also found. Further least-squares refinement including these hydrogen atoms reduced the R factor to 5.4%. In the present molecule, the cyclohexene ring has the normal half-chair conformation, and does not show the unusual behavior found in the p-bromobenzoate of 1,1,4aα-trimethyl-2α-hydroxy-8β-methoxy-1,2,3,4,4α,5,6,7,8,9-decahydrophenanthrene. The 8α-acetoxyl group, like the 8β-methoxyl group in the p-bromobenzoate, takes the axial orientation notwithstanding the inversion of the configuration. Such a conformation seems to be the preferred one for a cyclohexene ring which has a methoxyl or an acetoxyl group at the allylic position.
  • Norio Yui, Y\={o}ichi Kurokawa, Masami Nakayama
    1973 Volume 46 Issue 4 Pages 1027-1030
    Published: 1973
    Released: March 27, 2006
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    It has previously been reported that the dissociation of alkali halide and sodium nitrate between butanol and water phases could be explained reasonably if they were dissociated into free ions in each phase. The present investigation was undertaken to see to what extent dissociation occurs in the butanol phase. Conductometric measurements were carried out on solutions of LiBr, NaBr, NaCl, KCl, RbCl, and NaNO3 in the n-butanol–water system and on the solution of NaCl in the t-butyl alcohol–water system at 20°C or 25°C. These data were analyzed by using the Fuoss-Onsager equation for associated electrolytes, and the association constants were calculated to be as follows: NaBr 250, NaCl 600, KCl 610, RbCl 1850, NaNO3 180, and NaI 220 in the n-butanol–water (11 wt%) system at 25°C (except NaBr), and NaCl; 590, 160, and 75 for water wt% 30, 45, and 60 in the t-butyl alcohol–water system at 25°C, respectively. The association constants of NaCl in the t-butyl alcohol–water system were explained in terms of the simple electrostatic theory. The results were discussed briefly in comparison with conductance data reported in the literature.
  • Tetsuo Miyazaki, Terunobu Wakayama, Mitsuharu Fukaya, Yoshiyuki Saitak ...
    1973 Volume 46 Issue 4 Pages 1030-1035
    Published: 1973
    Released: March 27, 2006
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    The radiolysis of isobutane-propane (less than 5 mol %) or neopentane-alkane (5 mol%) mixtures has been studied at 77 K by means of ESR spectroscopy. When these alkane mixtures are γ-irradiated, the solute radicals are mainly formed by energy transfer from γ-irradiated isobutane or neopentane to the solutes. It is discussed whether the energy transfer is due to a proton transfer, a positive-charge transfer, or an excitation transfer, and it is concluded, for the following reasons, that the energy tranfser is probably due to the excitation transfer and that the excitation transfer may occur via highly-excited states of isobutane or neopentane; (i) The ionization potentials and the energies of the first singlet-excited states of the some additives are higher than those of isobutane or neopentane. (ii) The decrease in the solvent radical yields and the increase in the solute radical yields upon the addition of the solutes to the isobutane or neopentane amount approximately to 2–2.5 G-units. (iii) The yields of hydrogen increase sharply upon the addition of cyclopentane in the radiolysis of solid neopentane. (iv) It was concluded in previous studies that the formation of the solvent radical in the radiolysis of solid isobutane is due to the fragmentation of excited isobutane produced directly by γ-irradiation.
  • Mitsuharu Fukaya, Terunobu Wakayama, Tetsuo Miyazaki, Yoshiyuki Saitak ...
    1973 Volume 46 Issue 4 Pages 1036-1040
    Published: 1973
    Released: March 27, 2006
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    The effect of the matrix on the radiolysis of 2,3-dimethylbutane, neopentane. 2,2-dimethylbutane, and isobutane in the solid state has been studied at 77 K by means of ESR spectroscopy. Though only the ·CH2CH-(CH3)CH(CH3)2 radical is formed by the γ-irradiation of 2,3-dimethylbutane in the I crystal, the CH3\overset·C(CH3)-CH(CH3)2 radical is formed by the γ-irradiation of 2,3-dimethylbutane in the II crystal. Though the t-C4H9 and neo-C5H11 radicals are formed by the γ-irradiation of pure neopentane, the formation of radicals is affected appreciably by the addition of a small amount of alkanes. When neopentane containing ethane, etc. is γ-irradiated, the solute radical is mainly formed by energy transfer form the γ-irradiated neopentane to the solute. Most of the solutes have a spherical molecular structure like that of neopentane or are smaller than neopentane. When neopentane containing 3-methylpentane, etc. is γ-irradiated, only the neopentyl radical is formed. The molecular structures of the solutes are very different from that of neopentane. The formation of the solvent radical in the radiolysis of 2,2-dimethylbutane is affected by the addition of 3-methylpentane or methylcyclphexane. The formation of the butyl radical in the radiolysis of isobutane is also changed drastically by addition of alkanes. It is concluded that the formation of solvent radicals in the radiolysis of solid alkane is appreciably affected by the conditions of the matrix.
  • Isao Ando, Atsuo Nishioka
    1973 Volume 46 Issue 4 Pages 1040-1045
    Published: 1973
    Released: March 27, 2006
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    The temperature dependence of the proton chemical shift of n-pentane was calculated by the CNDO/2 method, taking into account the possible preferred conformations and the contributions from the diamagnetic, paramagnetic, and bond anisotropy terms. It was found that the bond anisotropy term contributes predominantly, while the diamagnetic term is not negligible, and that the paramagnetic term is negligible in comparison with these terms. The observed temperature dependence of the chemical shift can be reasonably explained by calculations using 570 cal/mol as the energy difference between the trans and gauche conformations, and also using 9.1×10−30 cm3 as the magnetic anisotropy of the C–C bond.
  • Shunsuke Kuribayashi
    1973 Volume 46 Issue 4 Pages 1045-1048
    Published: 1973
    Released: March 27, 2006
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    The crystals of meso-2,4-pentanediol borate are monoclinic with a space group of C2/c. There are eight molecules in the unit cell with dimensions of: a=15.36, b=13.53, c=7.68 Å, and β=113.3°. The crystal structure was determined by the X-ray method. The final discrepancy index is 0.121 for 1030 non-zero reflections. The molecule has a six-membered ring composed of one boron, three carbon, and two oxygen atoms. The borate group and the two carbon atoms of the pentane group are nearly co-planar. The five carbon atoms are also co-planar, and they are in trans positions. The molecule was proved to be of the meso type.
  • Hitoshi Mikuni, Azuma Takase, Motohiro Murano, Makoto Takahasi
    1973 Volume 46 Issue 4 Pages 1048-1053
    Published: 1973
    Released: March 27, 2006
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    The decomposition of ethylbenzene sensitized by Hg(3P1) was studied in gas phase. Hydrogen, methane and ethane were obtained as the main gaseous products. Their rates of formation were determined as a function of the pressure of ethylbenzene or xenon. To decide whether methyl or ethyl radical is the primary product in the photolysis, ethylbenzene-β-d1 was photolyzed. It was concluded that methyl radical is the primary product, since methane-d1 and ehane-d2 were obtained as products. A probable reaction mechanism is proposed to interpret the effect of pressure and light intensity on the rate of formation of ethane and methane. It is suggested that a biphotonic process is involved, which can explain the fact that the rate of formation of ethane is proportional to the square of light intensity.
  • Masahiko Suhara
    1973 Volume 46 Issue 4 Pages 1053-1055
    Published: 1973
    Released: March 27, 2006
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    The nuclear quadrupole resonance (NQR) frequencies of 35Cl in KClO3, AgClO3, Ba(ClO3)2·H2O, and Cu(ClO3)2·6H2O have been measured as a function of the temperature in the range from 77 to 350 K at a constant (atmospheric) pressure. These data have then been analyzed by the method of Brown. The torsional frequencies of the ClO3 ion in the crystals have been determined by fitting the experimental data with the Bayer theory, modified by taking into account the anharmonicity in torsional oscillation. The low barrier height obtained in Cu salt indicates that a freer rotational motion of the chlorate ion is to be expected in this crystal.
  • Masahiko Suhara, Ken-ichi Shimizu
    1973 Volume 46 Issue 4 Pages 1056-1060
    Published: 1973
    Released: March 27, 2006
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    The nuclear quadrupole resonance(NQR) of 35Cl in KClO3, AgClO3, Ba(ClO3)2·H2O, and Cu(ClO3)2·6H2O at room temperature has been measured by using a spectrometer system capable of reproducing with fidelity the line shape. The line-shape parameters were determined from the observed spectrum. All the line shapes of the four chlorates are of an intermediate character between Gaussian and Lorentzian. The line-width in K and Ag salts seems to originate from the inhomogeneity of the electric-field gradient, itself a result of the imperfection of the crystal. In Ba salt, it was found that the line-width is determined by the magnetic dipole-dipole interaction between chlorine and protons in the water of crystallization. The Lorentzian is the superior component of the line shape in Gu salt. This is explained in terms of the anharmonicity of the torsional oscillation of the ClO3 group.
  • Kinichi Obi, Jan W. Bottenheim, Ikuzo Tanaka
    1973 Volume 46 Issue 4 Pages 1060-1063
    Published: 1973
    Released: March 27, 2006
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    The photoreduction of 2-nitronaphthalene in 2-propanol has been studied at 313 nm. The photoreduction is suppressed in the presence of dissolved oxygen or a triplet quencher such as 1,3-cyclohexadiene. The results are consistent with the triplet state of 2-nitronaphthalene being the reactive species. 2-Naphthylhydroxylamine is formed as the reaction product. The quantum yield for the disappearance of 2-nitronaphthalene is estimated to be 0.037. The low quantum yield results from the slow reaction rate of hydrogen abstraction by the ππ* triplet state of 2-nitronaphthalene.
  • Teiichiro Ogawa, Masaharu Tsuji, Minoru Toyoda, Nobuhiko Ishibashi
    1973 Volume 46 Issue 4 Pages 1063-1067
    Published: 1973
    Released: March 27, 2006
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    Fluorobenzene, chlorobenzene, and bromobenzene were excited at a very low pressure in the vapor phase by a controlled electron beam of 60–300 V. Their emission spectra were then measured and compared with those excited by the photon. Fluorobenzene showed a characteristic photoemission of the parent molecule in the 260–320 nm region. The band was assigned to the transition from the lowest excited state to the ground state, and its shape did not vary appreciably with the energy of the electron beam. Though the spectrum had some features of “resonance fluorescence,” the vibrational structure of the band was not identical with that of any of the spectra obtained by photon impact between 4.7–4.9 eV. This seems to indicate that the molecule gave different spectra according to the excitation energy. However, the excitation by 60 V electrons and that by 300 V electrons did not produce any remarkable difference in the spectra under the resolution of the spectrometer used. Other aromatic halides failed to show any characteristic band of the parent molecules; instead, they showed weak lines due to Cl+ or Br+ and pronounced bands due to HCl+ or HBr+. This result was ascribed to the spin-orbit coupling effect and the predissociation of the excited parent molecules.
  • Akio Tajiri, Shohji Takagi, Masahiro Hatano
    1973 Volume 46 Issue 4 Pages 1067-1071
    Published: 1973
    Released: March 27, 2006
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    The ground-state electronic structure of biphenyl were studied by the use of the CNDO/2 method. It was found that the lengthening of the central C–C bond in biphenyl gave a reasonable minimum point for the potential energy curve. A modified version of the CNDO/2 method was used in order to calculate the electronic spectra of biphenyl for three possible (planar, angular, and vertical) conformations. The method gave a reasonable interpretation of the spectral features of biphenyl.
  • Hiroshi Fujimoto, Shigeki Kato, Shinichi Yamabe, Kenichi Fukui
    1973 Volume 46 Issue 4 Pages 1071-1076
    Published: 1973
    Released: March 27, 2006
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    Some perturbation equations for calculating the interaction energy of three independent systems have been derived in the frame of the simple Hückel MO approximation. The results of the numerical calculation of some typical interactions of three conjugated systems are presented in order to show the effect of the orbital symmerty upon the interaction energy. The role of the d orbitals of transition-metal catalysis olefin metathesis is examined.
  • Kasumi Ikegami, Naohiko Mikami, Mitsuo Ito
    1973 Volume 46 Issue 4 Pages 1076-1080
    Published: 1973
    Released: March 27, 2006
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    The polarized phosphorescence spectra of phenazine in phenanthrene was observed at 4.2 K. From the assignments of vibrations that were made on the basis of the results of polarized Raman spectra measurements for the single crystal, it was concluded that the possible mechanisms for the appearance of the vibronically-induced part of the spectrum are the following:
    (Remark: Graphics omitted.)
    Furthermore, it has been found that the vibrational modes which give rise to the more intense in-plane polarized bands are out-of-plane ring modes. These results seem to support the regularity found by Lim et al.
  • Akiko Okumura, Nobukazu Okazaki
    1973 Volume 46 Issue 4 Pages 1080-1084
    Published: 1973
    Released: March 27, 2006
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    The rate of oxygen exchange between selenate ions and solvent water has been measured by using oxygen-18 as a tracer. At 30°C in the concentration range of [H2SeO4]=0.57–1.5 M, and at 80°C in the region of pH=1.0–2.3, the rate may be expressed as R=k1[H+][HSeO4]. The values of the energy and entropy of activation are 23.1 kcal/mol and −5.0 e.u.(80°C) at pH=1.12, and 21.8 kcal/mol and −9.9 e.u.(30°C) at [H2SeO4]=1.64 M. An A–2 mechanism has been suggested for this path. Above ca 1.5 M H2SeO4, an additional rate term proportional to [H2SeO4]2 comes into play.
  • Akiko Okumura, Nobukazu Okazaki
    1973 Volume 46 Issue 4 Pages 1084-1088
    Published: 1973
    Released: March 27, 2006
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    The rate of oxygen exchange between selenite ions and solvent water has been measured at 0°C over the pH range of 8.7–12.5. The rate of exchange, R, may be expressed by the rate law;
    R=k1[SeO32−]+k2[HSeO3]+k3[HSeO3]2+k4[HSeO3][SeO32−].
    The observed rates were analysed in order to obtain the values of the rate constants. The over-all exchange reaction shows a negative salt effect; this has been shown to be an equilibrium salt effect on the dissociation of the hydrogen selenite ion.
  • Hiroshi Masuhara, Nobuyuki Tsujino, Noboru Mataga
    1973 Volume 46 Issue 4 Pages 1088-1093
    Published: 1973
    Released: March 27, 2006
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    The electronic spectra of some 1,2,4,5-tetracyanobenzene complexes in the lowest excited singlet state at 77 K were obtained by laser photolysis method. The observed spectra can be well reproduced with the superposition of the bands similar to those of acceptor anion as well as donor cation, independent of donors. Comparing the spectra with those of ionic radical salts, it is concluded that the electronic structure of these complexes is quite polar and the fluorescent state is a contact ion-pair. The electronic structures of excited electron donor-acceptor systems have been discussed, on the basis of the interaction between donor cation and acceptor anion. The chargetransfer degree in the excited complexes was found to increase in the following order; 1,2,4,5-tetracyanobenzenehexamethylbenzene complex in the phosphorescent state<hydrocarbon-amine heteroexcimers<the present complexes in the fluorescent state.
  • Setsuo Kashino, Masao Haisa
    1973 Volume 46 Issue 4 Pages 1094-1098
    Published: 1973
    Released: March 27, 2006
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    Isomorphous crystals of 5-chloro-7-iodo- and 5,7-dibromo-8-quinolinols have been examined by X-ray analysis. Both compounds crystallize in the monoclinic space group P2⁄a with four formula units in the unit cell. The cell dimensions are: a=16.98; b=4.16; c=14.84 Å, and β=112.0° for 5-chloro-7-iodo-8-quinolinol, and a=16.34, b=4.02, c=15.52 Å, and β=115.6° for 5,7-dibromo-8-quinolinol. The structure of the former, chinoform, has been determined by the Patterson methods from data collected with MoKα radiation on Weissenberg photographs, and refined by the block-diagonal least-squares method, with anisotropic temperature factors. The final R value is 0.081 for 836 observed reflections. The quinolinol molecule is nearly planar. In the crystals, the molecules related by two-fold axis are held together by hydrogen bonds to form bent dimers, which are stacked closely by van der Waals forces along the b axis.
  • Sadakatsu Nishikawa, Tatsuya Yasunaga
    1973 Volume 46 Issue 4 Pages 1098-1101
    Published: 1973
    Released: March 27, 2006
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    The ultrasonic absorptions of n-butylamine in aqueous solutions were measured at 25°C in the range of frequency from 15 to 220 MHz and of concentration from 0.698 to 3.00 M. The peak sound absorption was found. The mechanism of the observed peak sound absorption was attributed to the 4A\ ightleftharpoonsA4 reaction where A and A4 are the monomer and tetramer of the solute respectively. The rate constants of the forward and backward reaction were determined to be 2.2×106 M−3 sec−1 and 9.0×107 sec−1 respectively, and the standard volume change between the initial and final state in the reaction was calculated to be 14 ml mol−1.
  • Hiroatsu Matsuura, John Overend
    1973 Volume 46 Issue 4 Pages 1102-1106
    Published: 1973
    Released: March 27, 2006
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    The harmonic parts of the vibration-rotation interaction constants and the l-type doubling constants were calculated for CH3I and CD3I from the harmonic force field. The harmonic parts were subtracted from the experimental values to obtain the anharmonic parts which give relations among the cubic normal-coordinate force constants. Some of the individual values for the cubic force constants associated with the bending modes were obtained by using the derived relations and the previously estimated values for the stretch-stretch-stretch cubic force constants of the methyl group.
  • Harumi Endo
    1973 Volume 46 Issue 4 Pages 1106-1111
    Published: 1973
    Released: March 27, 2006
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    The sound velocity (V) and density of aqueous solutions of urea, dimethylurea, thiourea, acetamide, acetone, and dimethylformamide have been measured, and the adiabatic compressibility (β) has been calculated at various concentrations (μ: mole fraction). The β-μ curves and V-μ curves at various temperatures have a common intersection at the fixed concentrations of μcβ and μcV respectively. At these concentrations, the compressibility (βc) and the sound velocity (Vc) of a solution are independent of the temperature over a certain range. When βc is plotted against the mole ratio, rcβ=(water)/(solute) at μcβ, the plots for acetyl-derivatives fall on one straight line, and those for urea-derivatives, on another line. In the cases of acetone and ethanol, the rcβ values of these solutes coincide with the number of water molecules constituting the framework of the solid clathrate hydrate. Also, for the other aqueous solutions, it may be reasonable to conclude that the rcβ value corresponds to the number of water molecules constituting some other type of liquid-clathrate hydrate characteristic of each solute.
  • J. K. Vij, K. K. Srivastava
    1973 Volume 46 Issue 4 Pages 1112-1113
    Published: 1973
    Released: March 27, 2006
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    Measurements of relative permittivity were carried out at 30.0 °C in p-dioxane at 1 MHz and at 9.48 GHz for ortho (A), meta (B), and para (C) chloroanilines. The results are interpreted in terms of hydrogen bonding between amino hydrogens and the oxygen atoms of the dioxane molecule, the dipole moments and dielectric relaxation time values being given. The relative behaviour of chloroanilines has been discussed. It seems that a finite probability of H–Cl bond formation exists between one of the amino hydrogens and the neighbouring chlorine atom in o-chloroaniline.
  • Reikichi Iwamoto
    1973 Volume 46 Issue 4 Pages 1114-1118
    Published: 1973
    Released: March 27, 2006
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    Molecular and crystal structure of a 1 : 1 molecular complex of tetraethylene glycol dimethyl ether CH3O-(CH2CH2O)4CH3 (TGM) with mercuric chloride has been determined by means of X-ray diffraction. The complex has a monoclinic unit cell with a=14.29, b=15.10, c=7.84 Å, and β=97.0°. The space group is P21/n. Four molecules of both TGM and mercuric chloride are contained in the unit cell. The structure was determined by the ordinary heavy atom method. The molecular conformation of TGM in the complex is approximately
    CH3–O\undersetT–CH2\undersetG–CH2\undersetT–O\undersetT–CH2\underset\barG–CH2\undersetT–O\undersetT–CH2\undersetG–CH2\undersetT–O\undersetT–CH2\underset\barG–CH2\undersetT–O\undersetT–CH2\undersetG–CH2\undersetT–O–CH3,
    where T, G, and \barG indicate trans, gauche, and minus gauche forms, respectively. All the CH2–O bonds are trans, while the CH2–CH2 bonds are gauche and minus gauche in the adjacent chemical units. The conforma-tional unit of
    O\undersetT–CH2\undersetG–CH2\undersetT–O\undersetT–CH2\underset\barG–CH2\undersetT–
    was found to be very important and favorable for coordination between the O and Hg atoms. The molecule is circular but not closed, and the five oxygen atoms, which are nearly coplanar and located at the inner side of the circular molecule, enclose one HgCl2 molecule with close interatomic distances (2.78–2.96 Å) between the O and Hg atoms.
  • Reikichi Iwamoto
    1973 Volume 46 Issue 4 Pages 1118-1123
    Published: 1973
    Released: March 27, 2006
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    Structure of a 1:1 complex of tetraethylene glycol diethyl ether CH3CH2O(CH2CH2O)4CH2CH3 (TGE) with mercuric chloride has been investigated by means of X-ray diffraction. The complex has a cubic unit cell with a=−12.54 Å and four molecules of both TGE and HgCl2 are contained in the unit cell. The space group is Pa3-Th6. Four Hg atoms are located at the positions corresponding to the face centered arrangement. The TGE molecule is statistically arranged around the Hg atom located at the position having site symmetry \bar3. The following molecular conformation of TGE was suggested :
    CH3CH2\undersetT–O\undersetT–CH2\undersetG–CH2\undersetT–O2\undersetT–CH2\underset\barG–CH2\undersetT–O\undersetT–CH2\undersetG–CH2\undersetT–O\undersetT–CH2\underset\barG–CH2\undersetT–O\undersetG–CH2–CH3
    where T, G, and \barG indicate trans, gauche, and minus gauche forms, respectively. The TGE molecule encloses the HgCl2 molecule around the Hg atom with close interatomic distances between the Hg and O atoms.
  • Reikichi Iwamoto
    1973 Volume 46 Issue 4 Pages 1123-1127
    Published: 1973
    Released: March 27, 2006
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    Molecular and crystal structure of a 1:2 complex of hexaethylene glycol diethyl ether CH3CH2O(CH2CH2O)6-CH2CH3 (HGE) with HgCl2 has been determined by means of X-ray diffraction. The unit cell is monoclinic with a=23.34, b=7.84, c=16.69 Å, and β=115.0°. The space group is C2/c. The unit cell contains four HGE and eight HgCl2 molecules. The HGE molecule in the complex has the conformation
    CH3–CH2\undersetT–O\undersetT–CH2\undersetG–CH2\undersetT–O\undersetT–CH2\underset\barG–CH2\undersetT–O\undersetT–CH2\undersetG–CH2\undersetG–O\undersetG–CH2\undersetG–CH2\undersetT–O\undersetT–CH2\underset\barG–CH2\undersetT–O\undersetT–CH2\undersetG–O\undersetT–CH2\undersetG–CH2\undersetT–O\undersetT–CH2–CH3,
    where T, G, and \barG denote trans, gauche, and minus gauche, respectively, two HgCl2 molecules being coordinated with one HGE molecule. The asymmetric unit consists of a half of HGE and one HgCl2 molecule. The four oxygen atoms of either half of HGE, which are coplanar, are coordinated with one Hg atom with close interatomic distances (2.66–2.91 Å) between the O and Hg atoms, the central oxygen atom of HGE being coordinated with two Hg atoms. The HgCl2 molecule is distorted from the linear form by 4°.
  • Reikichi Iwamoto
    1973 Volume 46 Issue 4 Pages 1127-1129
    Published: 1973
    Released: March 27, 2006
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    Infrared spectra of CH3O(CH2CH2O)mCH3 (m=1–4) in their crystalline complexes with HgCl2 have been measured. There is no significant regular variation of band frequencies depending upon m. Molecular conformations of the compounds in the complexes have been concluded to be CH3–O\undersetT–CH2\undersetG–CH2\undersetT–O\undersetT–CH2\underset\barG–CH2\undersetT–O–CH3 for m=2 and CH3–O\undersetT–CH2\undersetG–CH2\undersetT–O\undersetT–CH2\underset\barG–CH2\undersetT–O\undersetT–CH2\undersetG–CH2\undersetT–O–CH3 for m=3 from molecular structures for m=1 and 4.
  • Akira Nakajima
    1973 Volume 46 Issue 4 Pages 1129-1134
    Published: 1973
    Released: March 27, 2006
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    The EPR of pure and diluted crystals of bis(2,2,6,6-tetramethylpiperidine-4)azine-1,1′-dioxyl (the TEMPAD biradical) was studied. From the spectra of the diluted cyrstal, the intra- and inter-molecular dipole-dipole interactions were identified. The crystal-field parameters of the intra-molecular coupling determined for the EPR spectra were: |D|⁄hc\simeq0.00477 cm−1 and |E|⁄hc\simeq0.00032 cm−1 and two kinds of principal axes were found. As the z-axis of the intra-molecular dipole-dipole coupling is in the direction connecting two N–O bonds in a molecule, the TEMPAD molecules in a unit cell may be said to occupy two different sites. The crystal-field parameters of the inter-molecular dipole-dipole coupling were determined to be: |D′|⁄hc∼0.012 cm−1 and |E′|⁄hc∼0.003 cm−1 and the z-axis of the tensor was in the direction of the a-axis. The assumed molecular-stack model could account for the aforementioned results. The EPR spectra of the pure TEMPAD biradical are one symmetrical Lorentzian line in all the directions; the angular dependence of the peak-to-peak linewidths was explained by means of the term of the inter-molecular dipole-dipole interaction obtained from the spectra of the diluted crystal using the three-dimensional Anderson-Weiss formula. The exchange parameter for the best-fit curve was of the order of magnitude of the weak exchange interaction estimated roughly from the small Weiss constant appearing in the paramagnetic susceptibility of the diluted crystals.
  • Toshinobu Imanaka, Yuriko Nitta, Shiichiro Teranishi
    1973 Volume 46 Issue 4 Pages 1134-1136
    Published: 1973
    Released: March 27, 2006
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    The relation between the poisoning effect on nickel and nickel boride catalysts in the liquid-phase hydrogenation of styrene and the bond strength of inhibitors on the catalysts has been studied by means of liquid-phase chromatography using a thermal detector. The results show that the sequence of poisoning effect is in agreement with that of the adsorption heat of inhibitors, and that the adsorption heat of each inhibitor on nickel boride is smaller than that on nickel. Besides, this sequence is also in agreement with that of the bond strength of the central metal ion and the coordinated ligand of some manganese complexes in a homogeneous system. These facts indicate that the adsorption energy of inhibitors on a catalyst in a heterogeneous system corresponds to the bond strength of the ligand coordinated to metal complexes in a homogeneous system.
  • Koichi Niihara, Toetu Shishido, Seishi Yajima
    1973 Volume 46 Issue 4 Pages 1137-1140
    Published: 1973
    Released: March 27, 2006
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    Compounds with the composition of RCo2B2 (R=La, Nd, Sm, Gd, Tb, Dy, and Y) were prepared by arcmelting methods. Their crystal structure was investigated by means of X-ray diffraction. These ternary rare earth borides crystallize in the tetragonal lattice. The lattice parameters are a=3.616±0.003 Å and c=10.215±0.005 Å for LaCo2B2 and a=3.561±0.002 Å and c=9.358±0.005 Å for YCo2B2. The good agreement between the X-ray diffraction intensities observed and those calculated shows that the ternary borides, LaCo2B2 and YCo2-B2, crystallize in the ThCr2Si2-type structure. The crystallographic data obtained for LaCo2B2 and YCo2B2 are as follows: space group 14/mmm(D4h17); 2R in 2(a), 4Co in 4(d), and 4B in 4(e) with z∼3⁄8. The boron atoms in this structure are situated at the center of a trigonal prism formed by four rare earth atoms and two cobalt atoms. We also found the RCo2B2 compounds to be isostructural with LaCo2B2 and YCo2B2, where R=Nd, Sm, Gd, Tb, and Dy. However, efforts to prepare CeCo2B2 and ErCo2B2 by arc-melting were unsuccessful.
  • Akio Yoshimura, Shunji Kato
    1973 Volume 46 Issue 4 Pages 1141-1144
    Published: 1973
    Released: March 27, 2006
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    It was found that the lumiflavin-sensitized photooxygenation of tryptophan in a dilute aqueous solution is greatly accelerated by the addition of adenine. This effect of adenine on the photosensitized oxygenation is specific for flavin dyes, and the quantum yield increases with the oxygen concentration at very low oxygen concentrations, but decreases at higher oxygen concentrations. Therefore, singlet oxygen can be excluded from the intermediates of this oxidative reaction. The oxygen adduct of the dye is considered to be a possible intermediate for the photooxygenation of tryptophan accelerated by adenine.
  • Siro Nagai
    1973 Volume 46 Issue 4 Pages 1144-1148
    Published: 1973
    Released: March 27, 2006
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    Ammonia-silica gel system was γ-irradiated at −196 °C. ESR spectrum observed from samples with low ammonia content showed a marked linewidth anomaly in the hf lines at −196 °C and changed with temperature reversibly. The free radical responsible for the spectrum was assigned to NH2 radical which undergoes a preferential rotation about an axis perpendicular to the radical plane at low temperatures and a substantially free rotation above −90 °C.
  • Tadaaki Inomata, Takao Moriwaki
    1973 Volume 46 Issue 4 Pages 1148-1154
    Published: 1973
    Released: March 27, 2006
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    Several divalent metal-aminobenzoic acid coordination compounds were prepared in aqueous solutions and their thermal analyses, magnetic moments, and infrared spectra were investigated. These coordination compounds have the structure of ML2 or ML2·nH2O and are coordinated with amino and carboxyl groups of the ligand. Metal-o-aminobenzoic acid chelates give approximately the same infrared spectra but metal-m- and p-aminobenzoic acid coordination compounds are classified into two groups by their infrared spectra. Detailed assignments for the infrared absorption bands of the metal-coordination compounds have been made by a comparison of the spectra with those of the ligand and its related compounds.
  • Yasumasa Ikezoe, Shoichi Sato, Akibumi Danno
    1973 Volume 46 Issue 4 Pages 1154-1158
    Published: 1973
    Released: March 27, 2006
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    The rate of formation of hydrogen cyanide from the nitrogen–ethylene system by 60Co gamma rays was found to depend on irradiation temperature, gas density, gas composition, and the nature of the wall surface of the reaction vessel. Above 100 °C, the G(HCN) value increased with the rise of temperature. Below 100 °C , the G(HCN) value remained constant down to −196 °C. In the temperature range from 400 °C to −196 °C, it increased with reduction of nitrogen gas density. The largest G(HCN) value obtained was 2.0. In certain cases, the wall surface influenced the suppression of hydrogen cyanide formation. As an active species responsible for hydrogen cyanide formation, excited nitrogen molecules are proposed in addition to nitrogen atoms. Excited nitrogen molecules are decomposed to nitrogen atoms with small activation energy or deactivated by collision with other molecules. They play an important role in cyanide formation at low pressures and at high irradiation temperatures.
  • Hiroaki Tagawa
    1973 Volume 46 Issue 4 Pages 1158-1161
    Published: 1973
    Released: March 27, 2006
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    The hydrogenation of uranium metal and the nitrogenation of uranium and its hydride with either nitrogen or ammonia have been studied using thermogravimetry. The reactions were examined at different pressures of hydrogen, nitrogen, and ammonia. The reaction of uranium with hydrogen takes place at 200°C and proceeds quickly above 210°C. The conversion curve depends greatly on the hydrogen pressure. In the reaction of the hydride with nitrogen, the weight gain occurs at about 160°C and becomes fast above 240°C. The reaction is shown to proceed in two steps: the formation of the mononitride and that of the sesquinitride. The reaction between uranium hydride and ammonia begins at 150°C and becomes rapid above 300°C. The reaction proceeds monotonously, and no step is observed. The nitrogenation behavior of uranium hydride with ammonia is found to be quite different from that in reaction with nitrogen.
  • Taketoshi Nakahara, Makoto Munemori, Sôichirô Musha
    1973 Volume 46 Issue 4 Pages 1162-1166
    Published: 1973
    Released: March 27, 2006
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    The atomic absorption spectrophotometric determination of beryllium in aqueous solutions and the effect of some water-miscible organic solvents were studied in a nitrous oxide-acetylene flame, using a Perkin-Elmer Model 303 atomic absorption spectrophotometer. The beryllium atomic absorptions were measured at the 234.9-nm resonance line of beryllium. The sensitivity for beryllium was 0.03 ppm for a 1% absorption. With the exception of palladium and silicon, none of the elements interfered with the determination of beryllium. Phosphoric acid caused an enhancement, while hydrochloric and nitric acids had a slight depressing effect. Furthermore, there seems to be a tendency for organic solvents with a higher ratio of the number of carbon atoms to that of oxygen atoms to cause greater enhancements in beryllium absorption, though there are a good number of exceptions. The atomic absorption method was applied to the determination of beryllium in several aluminum-, copper-, and magnesium-base alloys, with satisfactory results.
  • Taketoshi Nakahara, Makoto Munemori, Sôichirô Musha
    1973 Volume 46 Issue 4 Pages 1166-1172
    Published: 1973
    Released: March 27, 2006
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    The atomic absorption spectrophotometric determination of bismuth in aqueous solutions was established in premixed inert gas(entrained air)-hydrogen flames with a “multi-flame” burner in conjunction with a Nippon Jarrell-Ash Model AA-1 atomic absorption/flame emission spectrophotometer. Under the optimum operating conditions, a straight calibration graph was obtained at 223.1 nm in the concentration range of 0-10 ppm and the bismuth sensitivity for a 1% absorption was 0.1 ppm. The effects of acids and other elements on the bismuth atomic absorption were examined. Phosphoric acid caused a considerable depressing effect on the bismuth absorption. Hydrochloric acid remarkably depressed the bismuth absorption at acid concentrations lower than 0.5 N, but it gave no interference in acid concentrations higher than 0.5 N, in which water-insoluble bismuth oxychloride was quickly dissolved in hydrochloric acid. Hydrofluoric, nitric, perchloric, and sulfuric acids had no effect on the bismuth absorption. Most of the elements examined, with the exception of aluminum, boron, cerium, silicon, and zirconium, gave no interference to the bismuth absorption. The depressing interferences due to some elements were removed in appearance by adding a large amount (2000 ppm) of magnesium (as chloride). Furthermore, it was found that most of the depressing interferences could be eliminated by adding a large amount (0.1 M) of ammonium salts (as chloride or perchlorate) to the sample solutions. Bismuth in the presence of magnesium chloride, ammonium chloride, or ammonium perchlorate could be determined without interference from various other elements. The atomic absorption spectrophotometric method was applied to the determination of bismuth in sulfide ores, aluminum-, tin-, and lead-base alloys with satisfactory results.
  • Taketoshi Nakahara, Makoto Munemori, Sôichirô Musha
    1973 Volume 46 Issue 4 Pages 1172-1177
    Published: 1973
    Released: March 27, 2006
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    The atomic absorption spectrophotometric determination of titanium was subject to interference by other elements in a nitrous oxide-acetylene flame with a Perkin-Elmer Model 303 atomic absorption spectrophotometer, fitted with a 5-cm long-path slot burner. The effects of various other elements, acids, and water-miscible organic solvents on the titanium atomic absorption were examined. Aluminum produced the greatest enhancement of the titanium absorption of all the elements examined. Both butyric acid (2.0 M) and diethylene glycol mono-butyl ether (20%) enhanced the titanium absorption by about 100% in aqueous solutions. In the presence of 5000 ppm aluminum or 20% diethylene glycol monobutyl ether, the interferences from other elements appeared to be completely removed. Furthermore, the extraction of titanium with cupferron into methyl isobutyl ketone was successful in effecting an increase in the sensitivity of titanium and in eliminating, or at least diminishing the interferences from other elements. The atomic absorption method was then applied to the determination of titanium in ferric oxides, nickel-chromium steel, nickel alloy, and steels with satisfactory results.
  • Hiromitsu Moriya, Tatsuya Sekine
    1973 Volume 46 Issue 4 Pages 1178-1182
    Published: 1973
    Released: March 27, 2006
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    The distribution of zinc(II) was determined between 0.1 M constant-ionic-strength media containing sodium perchlorate and/or carboxylate ions, A, and carbon tetrachloride containing a neutral ligand, quinonline, Q, or the dimer of the same carboxylic acid, (HA)2. The distribution ratio was measured as a function of the concentration of carboxylate ions in the aqueous phase or of that of one of the above neutral ligands, in the organic phase. The extraction constant of the ZnA2 species in the caproic acid system was found to be KexA=[ZnA2]org/[Zn2+][A]2=10−0.15, while that in the valeric or butyric acid system was too small to be determined. The distribution ratio of zinc(II) increased with an increase in the concentration of the ligand in the organic phase. These increases were explained by the formation of adducts in the organic phase; in the caproate system, the species found were ZnA2Q, and ZnA2Q2, (β1(org)=[ZnA2Q]org/[ZnA2]org[Q]org=101.92, β2(org)=[ZnA2Q2]org/[ZnA2]org[Q]org2=102.84) or ZnA2(HA)42(org)=[ZnA2(HA)4]org/[ZnA2]org[(HA)2]Org2=102.92). No polynuclear species was found in these organic phases when the initial zinc(II) concentration in the aqueous phase was less than 10−3 M.
  • Tatsuya Sekine, Yoshihiro Takahashi
    1973 Volume 46 Issue 4 Pages 1183-1188
    Published: 1973
    Released: March 27, 2006
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    The solvent extraction of silver(I) in a 0.1 M constant-ionic-strength solution into chloroform with 2-thenoyltrifluoroacetone(TTA) and with caproic acid was studied by means of radiometry. It was found that these extractions are enhanced by the addition of aliphatic and cyclic alkenes, of aromatic hydrocarbons, and of some n-donors. The enhancement of the extraction was explained in terms of the formation of molecular complexes of the silver(I)-TTA chelate or of silver(I) caproate in chloroform. By an analysis of the experimental data, the stability constant of the silver(I)-TTA chelate in the aqueous phase, and the stability constants of the molecular complexes in the chloroform phase with these donors, were determined. Some consideration was made of these results and of the possibility of the application of these extraction systems to analytical chemistry.
  • Yuriko Unno, Goro Wada
    1973 Volume 46 Issue 4 Pages 1188-1195
    Published: 1973
    Released: March 27, 2006
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    The rates of the oxidation reactions of iron(II) to iron(III) by molecular oxygen in DMSO were measured under the catalyses of Cl, SCN, and en. The rate was proportional to the partial pressure of oxygen and was of the second order to [Fe(II)] in catalyses of Cl and SCN while it was of the first order to [Fe(II)] in catalysis of en. The reaction rate was also linear to [X]2 and [H+], where X represents Cl or SCN, indicating that the reaction proceeds via both the electron-transfer and hydrogen-atom-transfer mechanisms, side by side. The reaction order of [Fe(II)] depends upon which step is rate-determining among those of the oxygenation of Fe(II), its spontaneous decomposition, and its bimolecular reaction with another Fe(II) and, therefore, may be variable according to the concentrations of the reacting species. The autoxidation rate can be affected by the kinds of the catalyzing ligands. The autoxidation may be slow when an Fe(II) complex with low spin is oxidized to an Fe(III) complex with high spin and may be fast when from high spin type to low spin one. In the present cases of Cl, SCN, and en in DMSO, it seems to go from high spin type to high spin one with moderately large rates.
  • Keinosuke Suzuki, Hideshi Okuda
    1973 Volume 46 Issue 4 Pages 1195-1198
    Published: 1973
    Released: March 27, 2006
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    Fumaronitrile complexes, M(FMN)(AsPh3)2 (M=Pd, Pt and FMN=fumaronitrile), have been prepared. Various chelating agents replaced AsPh3 in the complexes, giving M(FMN)L (L is a chelating agent containing N, P, or As as donor atoms). The chemical shift of the methine protons of these complexes increased in the order:
    Pd–As<Pd–P<Pt–As<Pt–P.
    This is probably the increasing order of the π-back donation in these complexes. The UV spectra of the complexes are also described.
  • Ikuko Akaza, Takatoshi Tajima, Toshiyasu Kiba
    1973 Volume 46 Issue 4 Pages 1199-1204
    Published: 1973
    Released: March 27, 2006
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    A new scheme for the quantitative group separation of 19 common cations by reversed-phase extraction column chromatography has been devised. The following six columns, in which the organic solvent was adsorbed on Daiflone(polytrifluorochloroethylene), were prepared: a TBP–2N HCl column for Fe(III), Hg(II), and Sn(IV); a TOA(CCl4)–2N HCl column for Ag(I), Bi(III), Zn(II), and Cd(II); a TBP–6N HCl column for Sb(III); an AcAc(CHCl3)–pH 5.0 column for Cr(III) and Al(III); a TTA(MIBK)-pH 5.0 column for Cu(II), Co(II), Ni-(II), Pb(II), Mn(II), and Mg(II), and a TTA(MIBK)-pH 7.0 column for Ca(II), Sr(II), and Ba(II). After a test solution had been passed through the six columns successively in the above order, the metal ions are grouped and entirely retained on the specified columns.
  • Fujio Tsuchiya, Tsuneo Ikawa
    1973 Volume 46 Issue 4 Pages 1204-1208
    Published: 1973
    Released: March 27, 2006
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    The catalytic effect of the bismuth nitrate on the autoxidation of olefins has been investigated. Nitrogen dioxide, oxygen atoms, and bismuth oxynitrate, which are the thermal decomposition products of the bismuth nitrate, are not involved in the initiation of the reaction. The bismuth nitrate is only effective on olefinic compounds, not on saturated hydrocarbons, and it does not decompose hydroperoxide. The catalysis of the bismuth nitrate is supposed to result from direct interaction with olefin.
  • Mamoru Ai, Sadao Suzuki
    1973 Volume 46 Issue 4 Pages 1208-1211
    Published: 1973
    Released: March 27, 2006
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    The vapor-phase oxidation of various kinds of olefins, acids, aldehydes, etc. was carried out in a flow system over a series of MoO3–Bi2O3–P2O5 catalysts with different Bi/Mo ratios (P/Mo=0.2 atomic ratio) under fixed reaction conditions, in order to elucidate how the oxidation of these compounds is affected by the Bi2O3 content in the catalysts. The oxidation activity for these compounds varies in different individual manners as the Bi2O3 content increases. The results were interpreted successfully on the basis of the acid-base nature of the reactant and the catalyst. Then, the relationship between the character of the partial oxidations and the nature of the catalysts was discussed.
  • Hiroshi Horino, Takashi Toda
    1973 Volume 46 Issue 4 Pages 1212-1215
    Published: 1973
    Released: March 27, 2006
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    The reactions of 5-azidotropolone (I), its methyl ether (II), and tosylate (XIII) with active methylene compounds were investigated. Several tropolones and azulenes which possess the 1,2,3-triazole ring as a substituent were obtained. The order of reactivities in these reactions were found to be: tropolone tosyl groups>azido groups>tropolone methyl ether groups. The direction of the addition of the azido groups to active methylene compounds was also clarified.
  • Tomoo Miyazaki, Hiroyuki Shinoda
    1973 Volume 46 Issue 4 Pages 1216-1219
    Published: 1973
    Released: March 27, 2006
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    The dipole polarizabilities and the anisotropies of small linear molecules have been calculated according to a formula in which the frequency of the incident light is taken into account, as derived by the time-dependent perturbation theory. The wave functions and the energies were calculated by the CNDO method, involving the configuration interaction treatment. The effect of the parametrization in the CNDO method on the calculated polarizability and anisotropy has also been discussed. The method has been used to calculate the variations in the anisotropy, the polarizability, α, and its derivatives, (∂α⁄∂Si)0 and (∂2α⁄∂Si2)0, with the frequency of the incident light, where Si is the appropriate symmetry coordinate of the molecular vibration.
  • Akira Kasahara, Taeko Izumi, Minoru Yodono, Ryu-ichi Saito, Toru Taked ...
    1973 Volume 46 Issue 4 Pages 1220-1225
    Published: 1973
    Released: March 27, 2006
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    The Heck reaction of benzo[b]furan with arylpalladium chloride leads to the formation of 2-arylbenzo[b]-furan derivatives. In the presence of palladium acetate, benzo[b]furan reacts in benzene to give 2,2′-bibenzo[b]furyl, accompanied by 2-arylbenzo[b]furan. In the phenylation of [2-2H]benzo[b]furan with phenylpalladium salts, it was confirmed that no hydride shift takes place in the reaction. In the presence of palladium acetate, benzo[b]furan also reacts with olefin to produce benzo[b]furyl-substituted olefins, accompanied by a small amount of 2,2′-bibenzo[b]furyl, and from the reaction of [β,β-2H2]styrene and benzo[b]furan in the presence of palladium acetate it was confirmed that no hydride shift occurs in the reaction.
  • Hiroko Tada, Toshiaki Kakitani
    1973 Volume 46 Issue 4 Pages 1226-1232
    Published: 1973
    Released: March 27, 2006
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    We have developed Chipman’s kinetic study on a reaction of lysozyme and oligosaccharide. That is, we have analyzed how each catalytic rate constant affects the pattern of time-course graphs of oligomer concentrations in the reaction. By fitting computer simulation curves to three experimental time-course graphs, values of the catalytic rate constants for the bond-cleavage, transglycosylation and hydration are determined step by step. Also some binding constants are evaluated.
  • Koichiro Oshima, Tamio Shirafuji, Hisashi Yamamoto, Hitosi Nozaki
    1973 Volume 46 Issue 4 Pages 1233-1235
    Published: 1973
    Released: March 27, 2006
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    The reactions of the α-lithio derivative of diethyl methylphosphonate with various organic halides are described. The half-reduction of gem-dihalocyclopropanes has been achieved with this reagent. The same reagent gives bibenzyl and tetraphenylethane from benzyl bromide and benzhydryl chloride respectively. The deprotonation-metallation process is observed in the reactions of cinnamyl chloride and of trans-β-bromostyrene, in which 3-chloro-1,6-diphenyl-1,5-hexadiene and 1,4-diphenyl-3-buten-1-yne are produced respectively.
  • Noboru Yamazaki, Fukuji Higashi
    1973 Volume 46 Issue 4 Pages 1235-1238
    Published: 1973
    Released: March 27, 2006
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    Carboxylic acids were found to be activated by an oxidation mixture prepared from tri- and di-esters of phosphorous acid and mercuric chloride in a pyridine solution; they yielded the corresponding anilides upon treatment with aniline, together with a nearly quantitative yield of metallic mercury. The yield of the anilides was affected by the alkyl groups in the esters and by the tertiary amines. Only a small effect of the steric factor of carboxylic acids upon the reaction was seen in the cases of the diesters, and none at all was observed in the triesters. The reaction was proposed to proceed via the N-phosphonium salts of pyridines, which were not purely isolated, but which were assumed on the basis of the IR spectra.
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