Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 50 , Issue 1
Showing 1-50 articles out of 76 articles from the selected issue
  • Teiki Iwaoka, Michio Kondo
    1977 Volume 50 Issue 1 Pages 1-5
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    Flash photolytic photoionization of chlorpromazine hydrochloride has been investigated in several binary solvent systems, one component being always water. With changing solvent composition, the ionization yield in aerated state shows a convex curve. Opposite roles of oxygen toward photoionization have been found in aqueous and organic solutions: i.e. the deaeration causes an efficient ionization in organic solvents, but practically no ionization in water. A change in the reaction mechanism has been suggested in the mixed solvent with water content of about 85 %. It has been found that the photoionization proceeds monomolecularly via an excited state, the lifetime of which is far shorter than that of the lowest excited (π-π*) triplet state.
  • Takeshi Ohno, Shunji Kato, Akira Takeuchi, Shoichiro Yamada
    1977 Volume 50 Issue 1 Pages 6-9
    Published: 1977
    Released: April 19, 2006
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    For several different forms of N-salicylidenealkylamines (Schiff bases), the absorption and emission spectra, and the yields, lifetimes, and polarizations of the emissions were measured. The neutral Schiff bases exist in two forms, the enolimine and the ketoamine, in an alcoholic solution. All anions of the Schiff bases emit a moderate fluorescence at room temperature and a strong fluorescence and a very weak phosphorescence at 77K. Chelating to Zn2+ and Be2+, they strongly emit a fluorescence and phosphorescence similar to those of the free anions. In the bis-bidentate complexes, the phosphorescence increases and the fluorescence decreases compared to those of the mono-bidentatc complexes—this change in the emission yields may be due to the increase in the intersystem crossing rate, enhanced by an interaction between the ligands perpendicular to each other.
  • Tohr Yamanaka, Fumio Nakata
    1977 Volume 50 Issue 1 Pages 10-13
    Published: 1977
    Released: April 19, 2006
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    The kinetics in a liquid-phase isopropylation of m-cresol (I) with 9–25 kg/cm2 of propylene (VI) was studied at 240–280 °C over catalysts prepared from FeSO4 and γ-Al2O3. The rates of the formation of thymol (II) and 4-isopropyl-5-methylphenol (III) and the subsequent isopropylations of II and III were fitted to an irreversible, firstorder rate equation with respect to each starting material. All of the rate constants were roughly proportional to the 1.5th power of the surface acidity of 1≤H0≤3 of catalysts and the 2.2nd power of the pressure of VI. The apparent activation energies were 22 kcal/mol for Steps I→II, II→2,4-diisopropyl-5-methylphenol (V), and III→V and 6.5 kcal/mol for Steps I→III and II→2,6-diisopropyl-5-methylphenol (IV).
  • Shigeyoshi Sakaki, Nobuo Hagiwara, Noriko Iwasaki, Akira Ohyoshi
    1977 Volume 50 Issue 1 Pages 14-21
    Published: 1977
    Released: April 19, 2006
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    The parameters of a CNDO-type SCF-MO method are determined for some 5d transition metal complexes such as IrCl63−, AuCl4, and HgCl42− by comparing the calculated transition energies of these complexes with their experimental values. MO calculations with these established parameters are also carried out for IrBr63−, AuBr4, HgX42−, HgX2, and CH3HgX (X=Cl, Br, and I). The transition energies and assignments obtained from MO calculations are in fair agreement with experimental ones, with a few exceptions. This MO method gives successful results for the electron density and the bond strength: (1) a linear relation is obtained between the calculated and observed net charges on the Hg atom of HgX2 and CH3HgX, and (2) similar linear relations are obtained between the bond index EM–X values and the stretching force constant fM–X and between the EHg–C value and the fHg–C. Some discussion is presented for the Hg–C bonding character of the CH3HgX; the Hg–C bond is mainly contributed from the covalent interaction of the 6s and 6p orbitals of the Hg atom with the 2s and 2p orbitals of the C atom. The contributions of the Hg 5d orbitals and the electrostatic interaction are rather small.
  • Akira Itaya, Ken-ichi Okamoto, Shigekazu Kusabayashi
    1977 Volume 50 Issue 1 Pages 22-26
    Published: 1977
    Released: April 19, 2006
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    The migration of electronic excitation energy in films of poly(N-vinylcarbazole) (PVCz) prepared by the radical and cationic polymerizations(PVCz(r) and PVCz(c) respectively), poly[2-(9-carbazolyl)ethyl vinyl ether] (PCz-EVE), brominated PVCz(BPVCz), and poly(9-acryloylcarbazole) (PACz) has been studied by means of fluorescence-quenching experiments, using dimethyl terephthalate or perylene as a guest molecule. No clear difference in the concentration of the effective intrinsic trap sites was observed between PVCz(r) and PVCz(c) films. The concentration of the sandwich-like excimer site(cE) in a PVCz(r) film was nearly equal to that in a PVCz(c) film, while the concentration of the second excimer site (cS) in a PVCz(r) film was higher than that in a PVCz(c) film by a factor of about 1.6. The value of cE was much larger than that of cS for both films. The second excimer site seems to be a shallow trap. The number of carbazolyl chromophores covered by a singlet exciton during the lifetime was in the following order: PCzEVE>PVCz(r)≈PVCz(c)>PACz≈BPVCz. This order was explained by the concentration of the intrinsic trap sites depending on the distance between neighboring Cz chromophores, the lifetime of the singlet exciton, and the concentration of extrinsic trap sites.
  • Yoshiyuki Mido, Takashi Yamanaka, Ryoichi Awata
    1977 Volume 50 Issue 1 Pages 27-30
    Published: 1977
    Released: April 19, 2006
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    The fundamental N–H stretching absorptions of twenty nine N,N′-dialkylthioureas were observed in dilute solutions. The observed frequencies were classified into five groups assignable to the out, three different types of the trans, and the cis forms. The steric hindrance between the bulky t-butyl group and the thiocarbonyl sulfur, which is larger than for N,N′-dialkylureas, was suggested to cause the out form. Dialkylthioureas of RTUtB type seem to exist to a great extent in the trans-out conformation in solutions. It is suggested that it is not the N–H group with the bulky t-butyl group but the N–H group in the opposite part which is out of the skeletal plane. The energy difference between the out and the trans forms was found to be ΔH=430±100 cal mol−1.
  • Masakazu Anpo, Toshiaki Wada, Yutaka Kubokawa
    1977 Volume 50 Issue 1 Pages 31-35
    Published: 1977
    Released: April 19, 2006
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    The photolyses as well as the absorption spectra of adsorbed 3-methyl-2-butanone and 3-methyl-2-pentanone have been investigated in the presence and absence of nitrogen monoxide. The Stern-Volmer relationship was applied to the decrease in the rate of photolysis caused by addition of nitrogen monoxide. From the results together with those for acetone, 2-butanone, and 2-pentanone, it has been concluded that in the adsorbed layer the more blue shifted, i.e., the more strongly hydrogen bonded to the surface OH groups a ketone molecule, the shorter the lifetime of its excited state. It has been found that the lifetime of the alkyl radical on the surface increases with the decrease in its ionization potential, leading to the decrease in the strength of its interaction with the surface. Special features of the photolysis in the adsorbed layer have been described for 3-methyl-2-butanone photolysis.
  • Jiro Nakanishi, Tohru Takenaka
    1977 Volume 50 Issue 1 Pages 36-42
    Published: 1977
    Released: April 19, 2006
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    The polarized infrared and far-infrared spectra of the tetracyanothiophene (TCNT) crystals were recorded by means of the normal and oblique incidence of radiation upon the (001) and (20\bar1) sample planes. The Raman spectra of the powdered sample and of a saturated solution in acetonitrile or 1,2-dichloroethane were also obtained. The observed bands were experimentally classified into the symmetry species of the free molecule (the point group C2v) under the assumption of an oriented gas model. Assignments of the observed bands to individual fundamental vibrations were carried out with the aid of the spectral data of the analogous molecules and the normal coordinate analysis of the in-plane vibrations, which was made with a modified Urey-Bradley force field.
  • Tadayoshi Sakata, Mitsuo Hiromoto, Tomoko Yamagoshi, Hiroshi Tsubomura
    1977 Volume 50 Issue 1 Pages 43-48
    Published: 1977
    Released: April 19, 2006
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    The chemical reactions of the cation radicals of some aromatic diamines with their parent molecules, aliphatic amines or sodium hydroxide have been studied spectroscopically. In the case of the cation radical of p-phenylenediamine (PPD), the main products are Bandrowski’s base (BB) and PPD, p-benzoquinone diimine being found as an intermediate. This reaction are found essentially to be a disproportionation of PPD+ to BB and PPD in which bases added enhance the reaction rate. The thermodynamical quantities of the initial step of the reaction, proton transfer from PPD+, are estimated and the reaction mechanism is discussed. The reaction of the cation radical of N,N,N′,N′-tetramethyl-p-phenylenediamine (TMPD) with triethylamine (TEA) gives the parent molecule, TMPD. This reaction is concluded to be caused by an electron transfer from TEA to TMPD+ followed by a reaction of TEA with a large negative free energy change. The reaction between the cation radical of N,N-dimethyl-p-phenylenediamine and its parent molecule has also been studied.
  • Jun-ichiro Take, Masanori Ikeda, Yukio Yoneda
    1977 Volume 50 Issue 1 Pages 49-51
    Published: 1977
    Released: April 19, 2006
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    The influences of the degree of hydration of a silica–alumina surface on its Bronsted or Lewis acid content and on its catalytic activity for cis-2-butene polymerization were investigated at 30 °C as a function of the evacuation temperature. The raise in the evacuation temperature, i.e., the decrease in the degree of hydration, gave rise to an increase in both the Lewis acid content and the catalytic activity but to a decrease in the Bronsted acid concent. A good linear relationship, which could not be extrapolated through the origin, was found between the Lewis acid content and the catalytic activity. Thus, the conclusion is drawn that only strong Lewis acid sites are active in olefin polymerization on silica–alumina at low temperature.
  • Akira Itaya, Ken-ichi Okamoto, Shigekazu Kusabayashi
    1977 Volume 50 Issue 1 Pages 52-56
    Published: 1977
    Released: April 19, 2006
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    The emission properties of 9-ethylphenanthrene (EPh), poly(9-vinylphenanthrene) (PVPh), poly(9-phenanthryl methacrylate) (PPhMA), and poly[2-(9-phenanthryl)ethyl vinyl ether] were investigated in solution. These vinyl polymers showed no clear excimer fluorescence in the longer-wavelength region. Both the fluorescence quantum yield and the lifetime of PVPh decreased largely with an increase in temperature at higher temperatures. This suggests that PVPh forms an excimer which has a low fluorescence quantum yield. The fluorescence properties of PPhMA and PPhEVE, in which Ph chromophores are widely spaced on the skeletal chains, indicated little interaction between neighboring Ph chromophores in the singlet state. This results from the nature of Ph, in whith it is difficult to form an excimer. The phosphorescence spectrum and its lifetime of PPhEVE indicated a presence of a weak interaction between neighboring Ph chromophores in the triplet state. PVPh and PPhEVE showed a delayed fluorescence resulting from a T-T annihilation between two migrating triplet excitons.
  • Kazuhiro Niisawa, Ko Taki
    1977 Volume 50 Issue 1 Pages 57-59
    Published: 1977
    Released: April 19, 2006
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    The insertion reactions of recoil sulfur atoms produced by the nuclear transformation of 35Cl(n,p)35S process into the C–H bond of benzothiazole and the C–C bond of 2-methylbenzothiazole have been examined. It has been found that the C–H insertion is a little easier than the C–C insertion by the energetic sulfur atoms, and that in thermal reaction the water used as a solvent seems to have some role in producing the C–H insertion product.
  • Shun-ichi Ikawa, Kohji Fukushi, Kenji Fujiwara, Masao Kimura
    1977 Volume 50 Issue 1 Pages 60-64
    Published: 1977
    Released: April 19, 2006
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    The infrared band shapes of methyl iodide in solutions were simulated by the superposition of the Lorentzian functions. The a1-type band was well repoduced by a single Lorentzian function. Its half-width was reasonably explained by the reorientational and vibrational relaxations. The e-type band was reproduced by two Lorentzian functions; one represents the central main peak of the band, while the other is much broader and appears like a background. The half-width of the former was nearly proportional to the Q-branch line spacing in the gas spectrum, while that of the latter seems to be related to the A1-E-type Coriolis coupling.
  • Kiyoshi Arakawa, Kazuo Tokiwano, Kazumitsu Kojima
    1977 Volume 50 Issue 1 Pages 65-75
    Published: 1977
    Released: April 19, 2006
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    A new statistical thermodynamic theory is presented for a model of liquid water, which consists of two components, i.e., tetrahedrally-coordinated pentamers and non-hydrogen-bonded monomers. In the model the two components are assumed to be immersed in a uniform background potential which results from electrostatic, induction, and dispersion forces between water molecules. A partition function is given without assuming any specified lattice. A translational partition function is written into a simple and explicit expression which is derived from the Lebowitz solution of the Percus-Yevick equation for hard sphere mixtures. The mole fraction of each component and the density are determined by solving two equations, i.e., the condition of free energy minimization and the equation of state derived from the partition function, simultaneously. Various thermodynamic quantities are calculated and the values determined are compared with those observed. Some discussions are carried out, together with the criticism of the earlier theories.
  • Kazuhiko Ishizu, Masayoshi Ohnishi, Hideo Shikata
    1977 Volume 50 Issue 1 Pages 76-78
    Published: 1977
    Released: April 19, 2006
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    The ENDOR spectra of several alkylated biphenyl anions With para- and meta-substitutions were observed, and the relation between the molecular size and the optimum temperature of ortho-proton ENDOR were investigated in terms of the electron-nuclear dipole-dipole interaction. On the basis of the Stokes-Einstein model, a linear relation was found between the inverse of the effective radius and the cubic root of the η/T value at the optimum temperature of the ortho-proton ENDOR, under the assumption that the radical anion undergoes rotation accompanied by the solvent shell. In this situation, the separation between the radical anion and the counter cation thus estimated is more than 8.3 Å and the ion pair exists as a solvent-separated ion pair.
  • Shoko Yamadaya, Masaaki Oba, Yasuo Miki
    1977 Volume 50 Issue 1 Pages 79-82
    Published: 1977
    Released: April 19, 2006
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    The hydrocracking of tetralin was carried out over supported nickel–tungsten (NiO 3%, WO3 20%) on silica–alumina, alumina, and silica catalysts at a hydrogen pressure of 100 atm and in the temperature range from 325 to 375 °C. The total conversion of tetralin and the product composition of hydrocracking were measured for the catalysts. The influence of pretreatment of the catalysts with H2 and H2S on the conversion and product composition was investigated for each catalyst. The hydrocracking of decalin was also carried out under the same conditions. It is found that the hydrocracking of tetralin proceeds along two reaction paths: (A) hydrogenation to decalin followed by conversion to methylperhydroindenes and C10-naphthenes, (B) isomerization to methylindans followed by cracking to butylbenzene. The selectivity of each reaction path and the catalytic properties are discussed.
  • Kohji Hayase, Shigeo Hayano
    1977 Volume 50 Issue 1 Pages 83-85
    Published: 1977
    Released: April 19, 2006
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    The distribution coefficients, K, for 1-butanol, 1-pentanol, 1-hexanol, and 1-heptanol between the sodium dodecyl sulfate (SDS) micellar and aqueous phases were measured directly, with the gas chromatographic technique was used to measure the vapor pressure of the alcohols. The standard free energy change of penetration, ΔGp°, of the alcohol from the aqueous to the micellar phase was obtained using the equation: ΔGp°=−RTlnK. There is a linear relation between ΔGp° and the carbon number of the alcohol.
  • Kazumasa Maruyama, Hideshi Hattori, Kozo Tanabe
    1977 Volume 50 Issue 1 Pages 86-89
    Published: 1977
    Released: April 19, 2006
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    MoO3, SiO2, and SiO2–MoO3 of different compositions were prepared and their surface and catalytic properties examined. A large number of acid sites were generated by mixing SiO2 with MoO3, while each component oxide by itself did not exhibit any appreciable acidic properties. The oxidizing property of MoO3 was enhanced by mixing with SiO2. No new compounds were detected in the oxide mixture by X-ray diffraction. The activity for depolymerization of 2,4,6-trimethyl-1,3,5-trioxane correlated well with the surface acidity. In the isomerization of 1-butene, both MoO3 and SiO2–MoO3 were active. The active sites on MoO3 were poisoned by CO2 but not by NH3, while those on SiO2–MoO3 were poisoned by NH3 but not by CO2.
  • Minoru Ohki, Akio Takenaka, Hirotaka Shimanouchi, Yoshio Sasada
    1977 Volume 50 Issue 1 Pages 90-96
    Published: 1977
    Released: April 19, 2006
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    5-Bromocytosine and phthaloyl-DL-glutamic acid co-crystallize from their aqueous solution in space group P\bar1, with dimensions of a=10.578(2), b=19.640 (4), c=9.890 (3) Å, α=88.13 (2), β=107.86 (3), γ=104.26 (1)°. Two molecular complexes and one water molecule are in an asymmetric unit. The structure was solved by the heavy atom method and refined by a block-diagonal least-squares method. The 5-bromocytosine molecule binds with γ-carboxyl group of the amino acid through NH···O and OH···O hydrogen bonds. In spite of largely different molecular environment in the crystal from that of 5-bromocytosine:N-tosyl-L-glutamic acid complex, the mode of interaction between the nucleotide base and the amino acid is the same. Thus, it is suggested that the present geometry is a typical binding mode between cytosine and acidic side group of amino acid.
  • Azumao Toyota, Takeshi Nakajima
    1977 Volume 50 Issue 1 Pages 97-101
    Published: 1977
    Released: April 19, 2006
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    On the basis of the second-order Jahn-Teller theorem, we propose a criterion for predicting the stable groundstate geometrical structures of open-shell conjugated hydrocarbons. It is found that in contrast with the cases of the parent closed-shell hydrocarbons no molecular symmetry reduction occurs in the ion radicals of the CmHm–2 catacondensed nonalternant hydrocarbons, such as pentalene and heptalene. On the other hand, it is revealed that the ion radicals of fulvalene systems suffer the molecular symmetry reduction from D2h to C2v. In addition, the electronic spectra were calculated using the stable geometrical structures obtained by use of the semiempirical open-shell SCF MO method.
  • Issei Harada, Hideo Takeuchi, Masaaki Sakakibara, Hiroatsu Matsuura, T ...
    1977 Volume 50 Issue 1 Pages 102-110
    Published: 1977
    Released: April 19, 2006
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    The Raman spectra of butane, pentane, hexane, pentane-d12, and hexane-d14 and infrared spectra of pentane-d12 and hexane-d14 were measured for the liquid and solid states. The rotational isomerism of normal paraffins was studied on the basis of the spectral observations and the normal coordinate calculations. The spectra of the deuterated compounds were useful in the confirmation of the less stable isomers and the establishment of the local symmetry force field of normal paraffins. The enthalpy differences among the rotational isomers were studied on pentane and hexane, which yielded some important data for the study of the conformations and properties of longer hydrocarbons.
  • Masaaki Sakakibara, Hiroatsu Matsuura, Issei Harada, Takehiko Shimanou ...
    1977 Volume 50 Issue 1 Pages 111-115
    Published: 1977
    Released: April 19, 2006
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    The Raman spectra of ethyl methyl sulfide and its three deuterated compounds CD3SC2H5, CH3SCH2CD3, and CH3SC2D5 were measured for the liquid and crystalline states. The Raman spectra of the undeuterated species in the gaseous state were measured at different temperatures. The normal vibration frequencies were calculated by using a consistent set of force constants for aliphatic sulfides. The combination of the spectral observations of the deuterated compounds and the normal vibration calculations showed that only the gauche form exists in the crystalline state and the trans and gauche forms coexist in the liquid and gaseous states. The enthalpy difference between the gauche and trans forms in the gaseous state, ΔHG–T, was obtained as −30±50 cal/mol.
  • Yoshimi Kurimura, Hiroshi Saito, Ikuko Nakajima, Yuki Fujii
    1977 Volume 50 Issue 1 Pages 116-118
    Published: 1977
    Released: April 19, 2006
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    The second-order rate constants for the reduction of cobalt(III) complexes with a macrocylic Schiff-base ligand, Co(dop)L22+ (dop=N,N′-bis(2-hydroxyimino-1-methylpropylidene)-1,3-propanediamine and L=primary amine), by Fe (edta)2− are very sensitive to the nature of the axial ligands. The rate increases with a decreases in the basicity of the axial ligands: the order is methylamine, ethylamine, 2-aminoethanol, toluidine, aniline, and bromoaniline derivatives. It is shown that there is a linear relationship between the logarithmic second-order rate constant and the pKa of the axial primary amine ligand. Among the series of primary amine derivatives, the differences in the free energy of the activation for the reduction can be considered to be mainly dependent upon those in the enthalpy of the activation for the bond stretching of the Co–N (axial ligand) prior to the electron-transfer.
  • Yuzo Nishida, Shuhei Oshio, Sigeo Kida
    1977 Volume 50 Issue 1 Pages 119-122
    Published: 1977
    Released: April 19, 2006
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    New iron(III) complexes containing quadridentate Schiff bases, [Fe(L)AB]n+, were prepared, where H2L represents a quadridentate Schiff base, and A and B, unidentate ligands, such as imidazole, pyridine derivatives, and cyanide ions. The magnetic moments of the complexes are in the range of 1.9–6.0 B.M. at room temperature. Based on the magnetic susceptibilities at various temperatures (90–295 K), these compleses were classified into four types: (1) high-spin (S=5⁄2), (2) low-spin (S=1⁄2), (3) intermediate spin (S=3⁄2), and (4) cross-over complexes, the last of which have a ligand-field strength near the cross-over point of high-spin and low-spin types. From the ESR spectra obtained, the existence of a spin-equilibrium was established for the cross-over complexes.
  • Sukeo Onodera
    1977 Volume 50 Issue 1 Pages 123-126
    Published: 1977
    Released: April 19, 2006
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    This paper will describe gas chromatographic studies of the thermal decomposition of cobalt(III) ammine complexes in the solid state. The sample is pyrolyzed in a chamber in a helium atmosphere at a heating rate of 1 °C/min. The evolved products are directly led into a chromatographic separation column at periodic intervals of 10 °C. The preliminary gaseous product for these compound is ammonia. The gas evolution(GE) curves for each compound could be made as function of the temperature on the basis of the various gas chromatograms. These GE curves show two maximum peaks; the first is a sharp peak at about 250 °C, while the second is a broad peak in the 280–340 °C temperature range. The combination of these GE curves with the results of TG and DTA studies allows more complete interpretations of the thermal-decomposition reactions of the cobalt(III) ammine complexes.
  • Hisashi Okawa, Yuzo Nishida, Mitsunori Tanaka, Sigeo Kida
    1977 Volume 50 Issue 1 Pages 127-131
    Published: 1977
    Released: April 19, 2006
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    Hetero metal binuclear complexes, MM′ (fsaen)·nH2O (M=Cu(II) and Ni(II); M′=Cu(II), Ni(II), Co(II), Fe(II), and Mn(II); n=1–3), with N,N′-bis(3-carboxysalicylidene)ethylenediamine (H4fsaen) have been synthesized and characterized, where M and M′ denote the metal ion coordinated by the N2O2-coordinating atoms and the O4-coordinating atoms, respectively. The magnetism of CuNi(fsean)·3H2O and CuCo(fsaen)·3H2O is explained in terms of the Heisenberg model. The magnetism of NiCu(fsaen)·H2O, NiCo(fsaen)·2H2O, and NiMn(fsaen)·2H2O obeys the Curie-Weiss law, demonstrating the binuclear structure to be composed of one diamagnetic nickel(II) and one paramagnetic M′(II) ions. CuFe(fsaen)·2H2O, NiFe(fsaen)·2H2O, and CuMn(fsaen)·H2O each shows unusual magnetic property.
  • Kikuo Terada, Hiromi Honnami, Toshiyasu Kiba
    1977 Volume 50 Issue 1 Pages 132-137
    Published: 1977
    Released: April 19, 2006
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    A number of reducible compounds, such as nitrates, nitrites, nitro, nitroso, azoxy compounds, aldehydes, carbon tetrachloride, oximes, and chloramine T, can be determined by reducing them with chromium(II) ion prepared in an aqueous solution in a special vessel and measuring the absorbance of the resulting chromium(III) in the solution. In this reducing process, nitrate and nitrite are reduced to hydroxylamine quantitatively in hydrochloric acid at room temperature; carbon tetrachloride, nitrobenzene, and chloramine T each consume definite amounts of chromium(II) in an acidic medium at room temperature; propionaldehyde and azoxybenzene react with the reagent only in a basic solution; dimethylglyoxime and 1-nitroso-2-naphthol react only under heating at 80 °C in an basic medium. The absorbance of the resulting chromium(III) ion in the presence of the excess chromium(II) is found to obey Beer’s law at the wavelengths of 410–425 nm over the range of 4×10−3–8×10−2 mol/l of chromium(III). This concentration range corresponds to about 10−5–10−4 mol of the reducible compounds mentioned above. A rapid and precise method has been established with few disadvantages.
  • Fumio Hori, Keiji Matsumoto, Shun’ichiro Ooi, Hisao Kuroya
    1977 Volume 50 Issue 1 Pages 138-141
    Published: 1977
    Released: April 19, 2006
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    The triethylenetetraminepalladium(II) perchlorate and the potassium triethylenetetraminepalladium(II)tris-(hexafluorophosphate) were prepared; the X-ray structure analysis has been carried out for the latter compound. The crystal of [Pd(trien)](PF6)2·KPF6 is orthorhombic, with space group Pbca: a=21.645 (5), b=20.873 (5), c=9.541 (2) Å, and Z=8. The structure has been determined from X-ray diffractometer data and refined to R=0.091 (1166 reflections). The Pd atom has a planar coordination of 4N atoms disposed in a somewhat trapezoidal form. The complex cation has a pseudo symmetry plane which is perpendicular to the 4 N plane and bisects the H2N–Pd–NH2 angle. In the quadridentate triethylenetetramine ligand, each of the terminal H2N–CH2–CH2–NH– fragments forms a 5-membered chelate ring with the asymmetric envelope conformation, whereas the chelate ring formed by the middle –NH–CH2–CH2–NH– fragment has the symmetric envelope conformation. The electronic spectrum of [Pd(trien)]2+ is presented.
  • Yutaka Fukuda, Yukiko Miura, Kozo Sone
    1977 Volume 50 Issue 1 Pages 142-144
    Published: 1977
    Released: April 19, 2006
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    Ten new mixed copper(II) chelates containing N,N,N′,N′-tetraethylethylenediamine and various β-diketones were prepared and the cause of the large variations of νmax values observed in the visible absorption spectra of their organic solutions was discussed in comparison with similar variations of the corresponding tetramethyl chelates.
  • Yoichi Shimura, Katsuyuki Tsutsui
    1977 Volume 50 Issue 1 Pages 145-149
    Published: 1977
    Released: April 19, 2006
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    The characteristics of three-component phase diagrams consisting of water and a pair of enantiomeric or diastereomeric cobalt(III) complex salts have been clarified experimentally by constructing the solubility isotherms of the following 6 ternary systems at 25 °C: H2O–Δ-[Co(ox)(en)2]X–Λ-[Co(ox)(en)2]X, where X stands for Cl, I, (R,R)-C4H5O6–, Δ-[Co(edta)], 1/2[Sb2{(R,R)-C4H2O6}2]2− or d-C10H14OBrSO3−. It has been found that the latter two anions form an active racemate, rac-[Co(ox)(en)2]2[Sb2{(R,R)-C4H2O6}2]·5H2O and rao[Co(ox)(en)2](d-C10H14OBrSO3)·H2O, respectively. Solubility of the [Co(ox)(en)2]+ salts containing optically active counterions was determined at 5–60 °C in water.
  • Yoshiro Terai, Hiroaki Kido, Kazuo Kashiwabara, Junnosuke Fujita, Kazu ...
    1977 Volume 50 Issue 1 Pages 150-153
    Published: 1977
    Released: April 19, 2006
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    Platinum(II) complexes containing S,S- or R,R-trans-2-butene and various L-amino carboxylate, i.e. cis(N,olefin)[PtCl(L-prolinate)(S,S-trans-2-butene)] and trans(N,olefin)[PtCl(L-am)(S,S- or R,R-trans-2-butene)], were synthesized (L-am=L-prolinate, N-methyl-L-prolinate, N-benzyl-L-prolinate, L-alaninate and L-valinate). The kinetics of the inversion reaction of the coordinated S,S- or R,R-trans-2-butene was investigated in acetone in the presence of an excess of trans-2-butene at 8.0 °C. Second order rate law was obeyed with respect to the concentrations of the complex and free olefin, and no solvent path was observed. In the trans (N,olefin) complexes, interactions steric around the coordinated nitrogen atoms seems to be responsible in determining the ease of inversion via an associative mechanism. On the other hand, smaller rate for the cis(N,olefin) complex than the corresponding trans isomer seems to be due to the trans effect.
  • Thi Nga Nguyen, Yutaka Fukuda, Kozo Sone
    1977 Volume 50 Issue 1 Pages 154-157
    Published: 1977
    Released: April 19, 2006
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    Twelve mixed nickel(II) chelates with N,N′- or N,N-dimethyl (or diethyl)ethylenediamines and acetylacetonate ion (acac) were prepared, and their properties were compared with those of the similar chelates with N,N,N′,N′-tetramethyl(or tetraethyl)ethylenediamine. With the decrease of the number and bulkiness of the N-alkyl groups in the diamine, the tendency of forming 6-coordinated mixed chelates remarkably increases. The chelates of the type [Ni(diamine) (acac)]X, formed when X is B(Ph)4, which are essentially similar to the corresponding chelates with N,N,N′,N′-tetraalkylethylenediamines, but more apt to combine with solvent molecules and to go over into 6-coordinated structures than the latter.
  • Hidetake Kakihana, Masahiro Kotaka, Shohei Satoh, Masao Nomura, Makoto ...
    1977 Volume 50 Issue 1 Pages 158-163
    Published: 1977
    Released: April 19, 2006
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    The single-stage separation factors for boron isotopes between an ion-exchange resin and an external solution were determined, using an ion-exchange breakthrough operation. The lighter isotope boron-10 was considerably enriched in the anion-exchange resin phase. The separation factor was very much influenced by the boric acid concentration in the external solution, but not as much influenced by the kind of the anion exchange resin used and operation temperature. The separation factor increased with a decrease in the boric acid concentration of external solution from 1.008 (0.501 mol/l) to 1.016 (0.010 mol/l). The value of the separation factors obtained experimentally were compared with those estimated on the basis of the theory of the two-phase distribution of isotopes.
  • Tasuku Murakami, Ichiro Hirako, Masahiro Hatano
    1977 Volume 50 Issue 1 Pages 164-168
    Published: 1977
    Released: April 19, 2006
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    Circular dichroism (CD) and proton magnetic resonance (PMR) spectra of nickel(II) complexes containing a series of ethylenediamine-N,N′-diacetic acid (H2edda)-type optically active quadridentate ligands were measured in aqueous solutions. The epro complex which is an edda-type optically active ligand containing L-proline residues is found to exhibit the same CD spectrum as complexes of other edda-type ligands containing L-alanine, L-valine, L-phenylalanine, and L-serine residues. The CD and PMR spectra of the mixed complexes of these edda-type ligands having an oxalate ion was also measured. From the CD and PMR spectral data, it is concluded that these complexes stereospecifically take the Δ-s-cis form in solution. The large contact shift observed for the a protons of the amino acidate moieties indicates that the substituent groups become axial to the chelate plane.
  • Kentaro Anzai, Tsuneo Saita
    1977 Volume 50 Issue 1 Pages 169-174
    Published: 1977
    Released: April 19, 2006
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    Starting from 1,2: 5,6-di-O-isopropylidene-α-D-allofuranose (3a), the sugar portion of octosyl acids A and B (1a and 1b) was synthesised, though with some protecting groups. Compound 7a, thus obtained, was found to be acid-liable, and treatment of 7a in a dilute hydrochloric acid in methanol resulted in furanose-ring opening, affording an isopropylidene compound 8.
  • Kazutaka Arai, Michinori Oki
    1977 Volume 50 Issue 1 Pages 175-178
    Published: 1977
    Released: April 19, 2006
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    Exchange processes of diastereotopic protons of α-chlorodibenzyl sulfides were observed by means of dynamic nuclear magnetic resonance. Polar effects of solvents and substituent effects on the ease of the exchange process of protons in p,p′-disubstituted α-chlorodibenzyl sulfides indicate that the process occurs with the dissociation of the compounds into benzylic cations and chloride ion. It is possible to measure the rates of ionic dissocation by observing the change in the line shape of signals in 1H NMR spectra. The scope of the method is discussed.
  • Nobuo Mori, Tetsuo Takemura, Takayoshi Ohkuma
    1977 Volume 50 Issue 1 Pages 179-185
    Published: 1977
    Released: April 19, 2006
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    The intramolecular OH···π bonding, the probable conformations, and the internal rotation in two series of [n]paracyclophanols, I (1–4) and II (5–8), are investigated by means of IR, UV, and PMR spectroscopies. The IR results indicate that (1) there is the OH···π bonding in 1, 2, 3, 5, and 7 in CCl4, and (2) the integrated intensity ratio of the π-bonded OH species to the free OH, (Ab/Af), hardly changes in going from 1 to 3, while it decreases in going from 5 to 7. The ratio is, then, related to both ΔH and ΔS. In the PMR spectra, aliphatic-proton signals are assigned by means of the spin-decoupling and/or the shift-reagent technique; the results agree with those predicted, with a few exceptions. In the aromatic region, 3, 4, and 8 show singlets, while the others show AB-like quartets. These results are discussed in relation to the internal rotation of the benzene ring and/or the alkylene chain.
  • Giichi Goto
    1977 Volume 50 Issue 1 Pages 186-192
    Published: 1977
    Released: April 19, 2006
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    Steroidal cis-diol monoacetates (1,9,11, and 13) were refluxed with zinc powder in acetic acid to give the corresponding olefins (2,10,12, and 14) in good yield. Under the reaction conditions, no reaction occurred with diol diacetates (1b: R1=R2=H, R3=R4=Ac and 1m: R1=C6H5, R2=H, R3=R4=Ac) and trans-diol monoacetates (15 and 16). Acyclic erythro and threo diol monoacetates (17 and 19) underwent highly stereoselective reduction affording 18 and 20, respectively. The olefin-forming elimination proceeded with syn-elimination of a cyclic orthoacetate intermediate (21). The effect of some metals on the reduction and the behavior of a number of esters (26) and orthoesters (27) were also investigated.
  • Shuichi Ueda, Kazu Kurosawa
    1977 Volume 50 Issue 1 Pages 193-196
    Published: 1977
    Released: April 19, 2006
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    Seven 2-hydroxy-4-methoxybenzophenones were oxidized with manganese(III) acetate to give 9-xanthenones (24–65%). 2-Hydroxy-3′,4,4′,6-tetramethoxybenzophenone gave 1,3,6,7-tetramethoxy-9-xanthenone in a 5% yield. 2-Hydroxy-3′,4,4′,5-tetramethoxybenzophenone yielded 2,5-dihydroxy-3′,4,4′-trimethoxybenzophenone (9%). The oxidation of the 2-hydroxybenzophenones with lead tetraacetate also gave the 9-xanthenones, but in poor yields.
  • Hiroo Inoue, Nobuaki Inoguchi, Eiji Imoto
    1977 Volume 50 Issue 1 Pages 197-200
    Published: 1977
    Released: April 19, 2006
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    Sodium 1-benzyl-1,4-dihydronicotinamide-4-sulfinate (BNA-SO2Na) reacts with various halogen compounds, YZCHBr, through the cleavage of the carbon-sulfur bond to give sulfones, (YZCH)2SO2, in Y=Ph or PhCH=CH and Z=H; trans-stilbene in Y=Ph and Z=CH(Br)Ph or CH(OCH3)Ph; and the reduction products, YZCH2 and (YZCH)2, in Y=Ph, Z=Br, and Y=H, Z=PhCO. The BNA-SO2Na is converted to 1-benzylnicotinamide bromide, while sulfur dioxide or sulfite ions are formed.
  • Kunio Watanabe, Ken Inouye
    1977 Volume 50 Issue 1 Pages 201-206
    Published: 1977
    Released: April 19, 2006
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    The syntheses are described of two octadecapeptides, H–Val–Tyr–Pro–Asn–Gly–Ala–Glu–Asp–Glu–Leu–Ala–Glu–Ala–Phe–Pro–Leu–Glu–Phe–OH (Ip) and H–Val–Tyr–Pro–Asn–Gly–Ala–Glu–Asp–Glu–Ser–Ala–Glu–Ala–Phe–Pro–Leu–Glu–Phe–OH (Ih), corresponding to a tryptic fragment (positions 22–39) of porcine corticotropin (αp-ACTH) and that of human hormone (αh-ACTH), respectively. The porcine pep tide and the corresponding human peptide are prepared simultaneously by an identical synthetic procedure except for the introduction of amino acid residue in position 31. Synthetic peptide Ip is compared with the authentic αp-ACTH (22–39), which has been isolated from a tryptic hydrolysate of natural αp-ACTH, in terms of chemical and physicochemical properties to establish their identity. These data as well as those obtained with human peptide Ih prove the satisfactory synthesis of the two octadecapeptides.
  • Ken Inouye, Kunio Watanabe
    1977 Volume 50 Issue 1 Pages 207-210
    Published: 1977
    Released: April 19, 2006
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    An undecapeptide derivative, Z–Lys(Mhoc)–Pro–Val–Gly–Lys(Mhoc)–Lys(Mhoc)–Arg–Arg–Pro–Val–Lys–(Mhoc)–NHNH2, corresponding to the amino acid sequence 11–21 of corticotropin (ACTH)is synthesized. In the course of the synthesis a key intermediate H–Arg(NO2)–Arg(NO2)–Pro–OH is derived from Z–Arg(NO2)–Arg–(NO2)–Pro–OBzl by the treatment with hydrogen bromide in acetic acid. This procedure eliminates the danger of racemization associated with the use of alkali for saponification. The synthesis is also described of a nonapeptide derivative, Z–Lys(Mhoc)–Pro–Val–Gly–Lys(Mhoc)–Lys(Mhoc)–Arg(NO2)–Arg(NO2)–Pro–OH (amino acid sequence 11–19 of ACTH), in which a new protecting group, 9-methyl-9-fluorenyloxycarbonyl (Mfoc), is utilized for the temporary protection of an α-amino function.
  • Ken Inouye, Kunio Watanabe, Hideo Otsuka
    1977 Volume 50 Issue 1 Pages 211-219
    Published: 1977
    Released: April 19, 2006
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    The syntheses are described of two nonatriacontapeptides corresponding to the primary structure of porcine corticotropin (αp-ACTH) and that of human hormone (αh-ACTH). The porcine peptide is synthesized by assembling three fragment peptides corresponding to ACTH(1–10), ACTH(11–21) and αp-ACTH (22–39). The Synthetic product is compared with natural αp-ACTH in terms of chemical, physicochemical, and biological properties to establish their identity. The human peptide is synthesized via two different routes, one of which is the same as that employed for the synthesis of porcine peptide. The two synthetic preparations of human peptide are not only indistinguishable from each other, but also very similar to αp-ACTH in various items of physicochemical measurements and in the in vivo steroidogenesis assay. The collected data prove the satisfactory synthesis of αh-ACTH as well as αp-ACTH.
  • Sakae Uemura, Sakuya Tanaka, Masaya Okano
    1977 Volume 50 Issue 1 Pages 220-221
    Published: 1977
    Released: April 19, 2006
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    The treatment of various kinds of alkane- and arenethiols with thallium(III) acetate in chloroform at 20–30 °C readily affords the corresponding disulfides almost quantitatively, without affecting other functional groups, such as the hydroxyl, amino, and carboxyl in the thiols. Under similar conditions, the reaction of thiobenzoic S-acid with thallium(III) acetate gives thallium(III) thiobenzoate, while that of thioacetic S-acid yields diacetyl disulfide and thallium(I) thioacetate.
  • Yoshihiro Shigemasa, Yoshinobu Matsuda, Chikahiro Sakazawa, Teruo Mats ...
    1977 Volume 50 Issue 1 Pages 222-226
    Published: 1977
    Released: April 19, 2006
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    Under UV irradiation in the presence of an inorganic base, aqueous formaldehyde was found to give pentaerythritol and 2-hydroxymethylglycerol as the main products, accompanied by the concomitant formation of a mixture of sugars and sugar alcohols. The results indicate that this photochemical formose reaction is considerably different in product distribution from the thermal formose reaction using the Ca(OH)2 catalyst. The detailed examination of the photochemical formose reaction was carried out in the presence of Na2CO3, and a possible scheme for the formation of pentaerythritol and 2-hydroxymethylglycerol is proposed.
  • Shosuke Ito, Yoshimasa Hirata
    1977 Volume 50 Issue 1 Pages 227-230
    Published: 1977
    Released: April 19, 2006
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    The four 3,4-cis-stereoisomers of dimethyl dl-3-ethyl-4-methyl-1,2-cyclopentanedicarboxylates (1a, 1b, 1c, and 1d) have been synthesized and their configurations established. A comparison of the spectral data and the GLC behaviors has shown that the corresponding ester, one of the key degradation products of ikarugamycin, has the r-1, t-2, c-3, c-4-configuration (1a). The r-1, t-2, c-3, t-4-stereoisomer (1f) has also been prepared.
  • Kouji Okamoto, Kazuhiko Nonaka, Nobuo Izumiya
    1977 Volume 50 Issue 1 Pages 231-236
    Published: 1977
    Released: April 19, 2006
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    The synthesis of Tyrocidine A (TA), an antibiotic cyclic decapeptide, was achieved by a revised conventional method. Two analogs of TA, 6-glycine-TA and 7-glycine-TA, were synthesized by a similar method to investigate the contribution of L-phenylalanine6 and D-phenylalanine7 residues in TA to its antibacterial activity. The properties of synthetic TA were identical to natural TA. The antibacterial activities of the two analogs were weaker when compared with TA; the activity of 6-glycine-TA being weaker than 7-glycine-TA. The three cyclic peptides synthesized were subjected to droplet countercurrent chromatography (DCCC) and optical rotatory dispersion (ORD), and the elucidation of the difference in the activities between the two analogs was followed with DCCC and ORD.
  • Eizo Matsumura, Masahiro Ariga
    1977 Volume 50 Issue 1 Pages 237-241
    Published: 1977
    Released: April 19, 2006
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    The reactions of 3-bromo-4-nitro-2-R1-6-R2-5-X-pyridine N-oxides (1a:R1=H, R2=Me, X=H; 1b:R1=R2=Me, X=H; 1c: R1=R2=H, X=Br) with diethyl sodiomalonate, ethyl sodiocyanoacetate, and ethyl sodioacetoacetate have been carried out. The treatment of 1a, 1b, and 1c with diethyl sodiomalonate gives 3-[bis(ethoxycarbonyl)methyl]-4-nitro-2-R1-6-R2-5-X-pyridine N-oxides (2a, 2b, and 2c) and 4-[bis(ethoxycarbonyl)methyl]-3,5-dibromopyridine N-oxides (3c). With ethyl sodiocyanoacetate, 3-[cyano(ethoxycarbonyl)methyl]-4-nitro-2-R1-6-R2-pyridine N-oxides (4a and 4b) and 4-[cyano(ethoxycarbonyl)methyl]-3,5-dibromopyridine N-oxide (5c) are obtained. With ethyl sodioacetoacetate, 1a and 1c give 3-[acetyl(ethoxycarbonyl)methyl]-6-methyl-4-nitropyridine N-oxide (6a) and/or 3-ethoxycarbonyl-2-methyl-6-R1-7-X-furo[3,2-c]pyridine N-oxides (7a and 7c), but 1b is unaffected by ethyl sodioacetoacetate under the given conditions. The electronic and steric effects of methyl and bromo groups for the reactions are discussed.
  • Kiyoshi Iwai, Hiroshi Kosugi, Hisashi Uda, Mikio Kawai
    1977 Volume 50 Issue 1 Pages 242-247
    Published: 1977
    Released: April 19, 2006
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    A combination of the reaction of dianions of (phenylthio) acetic acid and its homologs with epoxides, the conjugate addition reaction of 3-phenylthio-2-(5H)-furanones with carbanion species, and the α-alkylation reaction of α-phenylthio-γ-butyrolactones is shown to provide a general method for the synthesis of a variety of substituted α-phenylthio-γ-butyrolactones. Oxidation of these α-phenylthiolactones to the corresponding sulfoxides, followed by pyrolysis furnishes all the types of substituted (3-, 4-, and 5-mono-; 3,4-, 3,5- 4,5-, and 5,5-di-; 3,4,5-tri-) 2(5H)-furanones in good overall yields.
  • Toshikazu Nagai, Tadao Shingaki, Hirokazu Yamada
    1977 Volume 50 Issue 1 Pages 248-253
    Published: 1977
    Released: April 19, 2006
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    It was found that cation radicals were formed from a number of substrates bearing a p-dimethylaminophenyl group, such as N,N,N′,N′-tetramethyl-p-phenylenediamine (TMPD) and N,N,N′,N′-tetramethylbenzidine (TMB), by reactions with o-sulfobenzoic anhydride (o-AH). The systems, bis(p-dimethylaminophenyl)methane (BMM) and tris (p-dimethylaminophenyl) methane (TMM) with o-AH, gave their cations in the presence of oxygen, showing that the oxygen eliminates the hydrogen atoms of the cation radicals derived from BMM and TMM. The reactions of N,N-dimethylaniline (DMA) with o-AH gave rise to isolations of BMM and N-methylaniline, along with the formations of the cation radical of TMB and the crystal violet cation (TMM+). The mechanisms of the reactions are proposed.
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