Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 53 , Issue 1
Showing 1-50 articles out of 70 articles from the selected issue
  • Hisao Yamashita, Yoshihiro Ozawa, Fumito Nakajima, Toshifumi Murata
    1980 Volume 53 Issue 1 Pages 1-5
    Published: 1980
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The mechanism of uranium adsorption from sea water by hydrous titanium(IV) oxide was investigated. The uranium adsorption experiments were conducted using a solution containing NaCl, NaHCO3, and uranium. Thermochemical calculation showed that the tris(carbonato)dioxouranate(VI) ion [UO2(CO3)3]4− found in sea water existed in the solution at pH 8 and 25 °C. The uranium uptake varied with the pH of the solution, exhibiting a minimum value at pH 8. The enthalpy change, ΔH, and the activation energy, E, of the uranium adsorption were found to be 23.6 kJ mol−1 and 52.7 kJ mol−1 respectively. The analysis of carbonate in the adsorbent showed that the carbonate ion in [UO2(CO3)3]4− was released into the solution during the uranium adsorption. On the basis of the present experimental results, the mechanism of uranium adsorption was discussed.
  • Kazushi Arata, Makoto Hino, Katsumasa Yabe
    1980 Volume 53 Issue 1 Pages 6-9
    Published: 1980
    Released: April 19, 2006
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    Alkylation was carried out at room temperature over catalysts prepared by calcination of FeSO4, Fe2O3, and Fe(OH)3 in the air at various temperatures and subsequent exposure to HCl at room temperature for 20 min. The FeSO4–HCl catalysts heat-treated at 700 and 750 °C showed very high activity and selectivity, the other catalysts except for the sulfate treated at 800 °C being almost inactive. The FeSO4(700 °C)–HCl catalyst was found to consist of FeCl3 and α-Fe2O3 by means of Mössbauer effect, the absorption peak areas being 14 and 86% for portions of iron based on the chloride and oxide, respectively. The results of DTA and TGA experiments suggest that the coordinate bond of water molecule on FeCl3 of the FeSO4(700 °C)–HCl catalyst is stronger than that on FeCl3 of the FeSO4 (600, 800, and 900 °C)–HCl and commercial FeCl3. The FeSO4(700 °C)–HCl catalyst showed a much higher activity than pure FeCl3. The iron(III) chloride formed by reaction of HCl and α-Fe2O3 obtained by thermal decomposition of the sulfate at 700 or 750 °C was found to be a very strong Lewis acid catalyst.
  • Shoji Kotake, Tsuyoshi Sei, Kunio Miki, Yasushi Kai, Noritake Yasuoka, ...
    1980 Volume 53 Issue 1 Pages 10-14
    Published: 1980
    Released: April 19, 2006
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    The crystal structure of [{Pd(acac)(NHEt2)2}+(acac)] at −170°C was determined by means of X-ray diffraction. The crystal belongs to monoclinic system: a=13.905(3), b=12.901(4), c=12.205(3) Å, β=96.28(2)°, space group I2/c with Z=4. The structure was established by the heavy atom method and refined anisotropically by the least-squares procedure; R=0.044 for 1558 non-zero reflections. Both the {Pd(acac)(NHEt2)2}+ cation and (acac) anion lie on the crystallographic two-fold axis. The cation and anion lying on the same two-fold axis are bound together by two hydrogen bonds [N–H···O(2)=N′–H′···O(2′)=2.871(4) Å] to form an ion-pair. Two ion-pairs mutually related by the crystallographic center of symmetry make a packing unit of the crystal.
  • Tetsuo Higashihara, Ko Saito, Ichiro Murakami
    1980 Volume 53 Issue 1 Pages 15-18
    Published: 1980
    Released: April 19, 2006
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    The disappearance rate of S2, which was produced from the pyrolysis of COS, was measured behind incident shock waves by monitoring the UV emission in the temperature range of 4500–6000 K and in the pressure range of 0.32–0.5 atm. It was found that two processes could possibly account for the disappearance of S2:
    S_2+Ar→2S+Ar\ ag3
    and
    (Remark: Graphics omitted.)
    and the following rate equation was obtained:
    -d[S_2]/dt=k_II[S_2][Ar]mol cm^-3s^-1
    where
    k_II=10^13.68exp(-77kcal/RT)cm^3mol^-1s^-1.
  • Hisashi Uedaira, Hatsuho Uedaira
    1980 Volume 53 Issue 1 Pages 19-21
    Published: 1980
    Released: April 19, 2006
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    The diffusion coefficients of magnesium 1,2-ethanedisulfonate and magnesium 1,4-butanedisulfonate in aqueous solutions have been measured at 25 °C. The concentration dependence of the diffusion coefficients of these salts was larger than those of the corresponding sodium salts. It has been shown that the 2:2 bolaform electrolyte behaves approximately like an ordinary 2:2 electrolyte. From these and previous results, it has been concluded that the diffusion behavior of bolaform electrolytes distinctively depend on the valency of the counterion.
  • Hideo Ueda, Chuji Katayama, Jiro Tanaka
    1980 Volume 53 Issue 1 Pages 22-25
    Published: 1980
    Released: April 19, 2006
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    The crystal and molecular structure of γ-metasantonin has been determined by the X-ray method. The crystal is orthorhombic, P212121, with lattice parameters a=10.371(1), b=7.904(1), c=15.975(1) Å. The molecule has two independent α,β-unsaturated ketone chromophores which take a chiral configuration. The chromophores show good planarity. A/B ring fusion is cis.
  • Tetsuo Morimoto, Toshie Kadota, Hiroshi Yanazawa, Shigeharu Kittaka
    1980 Volume 53 Issue 1 Pages 26-29
    Published: 1980
    Released: April 19, 2006
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    Spherical particles of silica were prepared by passing fine silica material through the O2–H2 flame. Spherical particles obtained were amorphous, creviceless, and very large in size compared to those of the starting material which indicates that spheres are made by complete comelting of a large number of fine particles. Water adsorption measurements showed that the rate of rehydration of the dehydroxylated silica surface is very slow, especially at low water pressures, and that the spherical silica has a heterogeneous surface, this heterogeneity being enhanced when the sample is heated at elevated temperatures. The ratio of the number of water molecules adsorbed in the first physisorption layer to that of the underlying surface hydroxyls was found to be 1:1.
  • Noriaki Hirayama, Kunikatsu Shirahata, Yuji Ohashi, Yoshio Sasada
    1980 Volume 53 Issue 1 Pages 30-35
    Published: 1980
    Released: April 19, 2006
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    An X-ray analysis of the α form of L-glutamic acid, C5H9NO4, has been carried out. The space group is P212121 with a=7.068(1), b=10.277(1), c=8.755(1) Å and Z=4. The structure was solved by the direct method, and least-squares refinement using 855 reflexions led to the final R value of 0.034. The molecule is in a zwitter ion form, and there is a strong OH···O intermolecular hydrogen bond with the O···O distance of 2.578(2) Å. The conformation of L-glutamic acid in the α form is quite different from that in the β form. The occurence frequency in various crystal structures containing glutamic acid residues shows that the conformation in the β crystal is more stable and favourable than that in the α crystal. The transition of the α form to the β form of L-glutamic acid in the mother liquor and the conditions for obtaining the α crystals are discussed based on the crystal and molecular structures of the two polymorphs.
  • Kenji Yokoyama, Shiro Maeda, Chisumi Etoh, Susumu Matsuzaki, Koichi To ...
    1980 Volume 53 Issue 1 Pages 36-38
    Published: 1980
    Released: April 19, 2006
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    The resonance Raman spectra of TCNE-M+ (M=Na, K, Rb, Cs) in MTHF solutions have been measured at 100 K by exciting radiations within the long wavelength absorption band characteristic of the dimer (TCNE)2. Two remarkably resonant lines have been observed at about 180 cm−1 and 150 cm−1, showing an obvious change of the relative intensity depending on the counter cation species. The resonance behavior definitely indicates that the stretching vibration of interradical bond is responsible for these lines. Formation of two different types of dimer salts has been proposed as the most probable interpretation of the observed spectral behaviors.
  • Yoshio Sakaguchi, Hisaharu Hayashi, Saburo Nagakura
    1980 Volume 53 Issue 1 Pages 39-42
    Published: 1980
    Released: April 19, 2006
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    The external magnetic field effects upon product yields in the singlet sensitized photolysis of dibenzoyl peroxide in toluene were studied. The observed field dependencies were classified into four types, and were interpreted in terms of the electronic Zeeman and hyperfine interactions in the intermediate radical pair. Especially large magnetic field effects were observed for the yields of dimethylbiphenyls, new products in this reaction.
  • Hiroyuki Ohtani, Takayoshi Kobayashi, Kaoru Suzuki, Saburo Nagakura
    1980 Volume 53 Issue 1 Pages 43-47
    Published: 1980
    Released: April 19, 2006
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    The build-up time constants of Tn←T1 transition bands were measured with 4-hydroxybenzophenone, Michler’s ketone, 2-nitrofluorene, 1-nitropyrene, and 9-nitroanthracene in solution with the aid of picosecond spectroscopy. All the compounds exhibit fast build-up of the Tn←T1 absorption with the time constants smaller than 100 ps. The picosecond kinetics of these nonfluorescent compounds are interpreted in terms of the electronic structures of initial and final states relevant to radiationless transitions.
  • Yoshiaki Hamada, Masamichi Tsuboi, Hideaki Umeyama
    1980 Volume 53 Issue 1 Pages 48-52
    Published: 1980
    Released: April 19, 2006
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    Ab initio molecular orbital calculation has been applied to hydroxylamine molecule to reach a reliable set of force constants by the use of the 4-31G basis set. This approach was found to be an enlightening way to solve a problem of the so far undeterminable amino twisting frequency. For this, the value of 1250±100 cm−1 was estimated. A few comments are also given on the theoretical and experimental values of force constants.
  • Tadashi Kato, Katsuaki Yano, Tsunetake Fujiyama
    1980 Volume 53 Issue 1 Pages 53-57
    Published: 1980
    Released: April 19, 2006
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    Light scattering spectra have been observed for binary solutions of acetic acid and carbon tetrachloride at several concentrations and temperatures. The Rayleigh intensities were reduced to concentration fluctuations. The observed concentration and temperature dependencies of concentration fluctuation were interpreted by assuming association equilibria involving both cyclic dimers and linear polymers. The simultaneous measurement of concentration and temperature dependencies of concentration fluctuation are necessary to determine local structures in solutions where different types of local structure coexist.
  • Yoshio Matsumoto, Michiko Shirai, Takeshi Kawashima
    1980 Volume 53 Issue 1 Pages 58-60
    Published: 1980
    Released: April 19, 2006
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    A new type of system was prepared which consisted of a water-soluble macromolecular metal complex caged in the network structure of a gel particle, the caged reagent being soluble in nature in an aqueous solution, but unable to get out of the gel particle into the outside solution by going through the network because of its large molecular size. This system was further proved to be useful as a convenient capturer of heavy metal ions in an aqueous solution.
  • Okio Nomura, Suehiro Iwata
    1980 Volume 53 Issue 1 Pages 61-67
    Published: 1980
    Released: April 19, 2006
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    The ethyl radical formation from hydrogen and ethylene was studied with ab initio open shell SCF and CI methods. At first, the minimal basis set (STO-6G) was used to determine a minimal energy path. The calculated exothermicity and the height of the barrier were 72.3 kcal/mol and 16.9 kcal/mol, respectively. After the full geometry optimization with the double zeta basis set the calculated exothermicity became 38.3 kcal/mol, which is in agreement with the experimental value (40.1 kcal/mol), but the barrier height (16.5 kcal/mol) was no better than that obtained by the minimal basis set. After the extensive CI calculations along Sloane and Hase’s path with the minimal basis set, the calculated height of the barrier became only 5.1 kcal/mol. The small but finite barrier height is important in this reaction. The successive hydrogenation to form ethane was also studied and no barrier was found in the reaction.
  • Masaru Nakahara, Yoshio Kumo-oka, Jiro Osugi
    1980 Volume 53 Issue 1 Pages 68-71
    Published: 1980
    Released: April 19, 2006
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    Conductivities of HCl and KCl in methanol containing traces (0.12 to 0.40 mol%) of water have been measured in the concentration range of ≈0.4 to ≈5 mmol dm−3 at 25 °C up to 2000 kg cm−2. The limiting equivalent conductance (Λ°) for HCl and KCl decreased with increasing pressure. The excess proton conductance due to the proton-jump mechanism has been measured by Λ°(HCl)−Λ°(KCl) and found to increase with increasing pressure in nearly and absolutely pure methanol. The acceleration of proton jumps by pressure indicates that the rotation of methanol molecules about the longer molecular axis becomes faster at higher pressure. This anomaly is attributed to distortion with pressure of hydrogen bonds in methanol and to an increase in the repulsive field exerted by the proton on the molecule to rotate.
  • Yasuyuki Takeda, Hisao Yano, Masayuki Ishibashi, Hiroshi Isozumi
    1980 Volume 53 Issue 1 Pages 72-76
    Published: 1980
    Released: April 19, 2006
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    The formation constants, KML+, for 1:1 complexes of 15-crown-5 (15C5), 18-crown-6 (18C6), and dibenzo-24-crown-8 (DB24G8) with alkali metal ions and the limiting ionic molar conductivities, λ°, of the complexed cations in propylene carbonate have been determined at 25 °C conductometrically. The KML+ value series about the same alkali metal ion among the crown ethers are given in the order 18C6>>DB24C8>15C5. The KML+ sequences of the alkali metal ions with 15C5, 18C6, and DB24C8 are Li+>Na+>K+>Rb+>Cs+, K+>Na+>Rb+>>Cs+, and Na+>K+>Rb+≥Cs+, respectively. The indication is that the ability of the alkali metal ions to form complexes with the three crown ethers is not always affected primarily by the relative sizes of the alkali metal ions and the crown ether cavity. In each case of 18C6 and DB24C8 the λ° values of the alkali metal ions are nearly equal, while in the case of 15C5 there are considerably differences, suggesting that in the former case the charge of the alkali metal ion trapped in the crown ether cavity is effectively shielded. This is not true in the latter case.
  • Toshishige M. Suzuki, Tetsuo Kimura, Junnosuke Fujita
    1980 Volume 53 Issue 1 Pages 77-81
    Published: 1980
    Released: April 19, 2006
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    The optically active ligands, (2S,7S)-2,7-di(2-pyridyl)-3,6-diazaoctane (S,S-peaen) and (2R,8R)-2,8-di(2-pyridyl)-3,7-diazanonane (R,R-peatn) have been prepared. The dichlorocobalt(III) complexes of these ligands have been prepared and several isomers isolated. The ligand, S,S-peaen yielded one cis-α and two types of cis-β isomers, while the R,R-peatn gave only one cis-β isomer. Oxalato and dinitro derivatives of the R,R-peatn complexes have been isolated and characterized and the stereochemistry of the isolated complexes discussed.
  • Hiroaki Kido
    1980 Volume 53 Issue 1 Pages 82-87
    Published: 1980
    Released: April 19, 2006
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    Tris(acetylacetonato[2-14C])-cobalt(III), -chromium(III), -ruthenium(III), and -rhodium(III) undergo ligand exchange in acetylacetone (Hacac) at 85–190 °C without decomposition of the complexes. The exchange rate is proportional to the complex concentration, and the first-order rate constant k0 decreases in the sequence Co(III)>Cr(III)>Ru(III)>Rh(III), k0⁄10−5 s−1 being 2.4 (93 °C), 5.6 (117 °C), 9.5 (158 °C), and 2.4 (185 °C), respectively. The activation enthalpies and entropies and deuterium isotope effect on k0 are significantly different between the Co(III) and the Cr(III), Ru(III) and Rh(III) complexes. An intermediate involving an one-ended acetylacetonate and a solvent molecule(Hacac) is concluded to be formed in the rate-determining step. The SN1 and the SN2 mechanism are assigned to the exchange reactions of the Co(III) complex and the others, respectively, for the rate-determining steps.
  • Daijiro Yamamoto, Masamichi Tsukada, Yasuaki Hirota, Haruo Mizuno
    1980 Volume 53 Issue 1 Pages 88-90
    Published: 1980
    Released: April 19, 2006
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    Potassium salt of α,α′-bis(dithiocarboxyoxy)-p-xylene (abbreviated as K2-XDX) was synthesized as a chelating agent with p-xylene-α,α′-diol, carbon disulfide, and potassium hydroxide. Since a mercury(II)–XDX chelate complex suspension scattered pearl-blue light strongly because of the formation of a colloidal solution, the nephelometric analysis of small amounts of mercury(II) was undertaken. The calibration curve was found to be linear in the two ranges of 0.03–1.00 and 0.50–25.00 μg cm−3 of the mercury(II) ion respectively, but no suitable masking agents for interfering metal ions were found. The mole ratio of mercury(II) to XDX in the complex was found to be 1 to 1. These data for the complex suggested that XDX and mercury(II) combined alternately to form the (–Hg–XDX–)n complex. The molecular weight of this complex could be calculated as about 2×107 from the Zimm plot on the basis of the light-scattering method.
  • Tamizo Kogane, Reiko Hirota
    1980 Volume 53 Issue 1 Pages 91-95
    Published: 1980
    Released: April 19, 2006
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    The reactions of bis(β-diketonato)copper(II) with pyrazole and imidazole gave the diazole adducts Cu(β-dik)2(Hdzl) (β-dik=β-diketonate anion; Hdzl=diazole) and/or the μ-diazolato complexes [Cu(β-dik)(dzl)]n (n=2,4,….). The complexation reactions are very sensitive to the nature of the diazole and to the reaction conditions, sometimes giving different products depending upon the solvent used. In chloroform, Cu(β-dik)2-pyrazole and Cu(β-dik)2-imidazole complexes exhibited characteristic absorption maxima at approximately 570 and 555 nm, respectively, which are much shorter than the λmax values of the starting Cu(β-dik)2 chelates.
  • Yoneichiro Muto, Tadashi Tokii, Michio Nakashima, Michinobu Kato, Hans ...
    1980 Volume 53 Issue 1 Pages 96-100
    Published: 1980
    Released: April 19, 2006
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    Three modifications of dichloro[2-(hydroxymethyl)pyridine N-oxide]copper(II), CuCl2(2-CH2OH·pyo), were prepared and characterized by the temperature dependences of their magnetic susceptibilities and their IR spectra. The greenish-yellow modification shows ferromagnetic behavior (θ⁄K=+20), whereas both the yellow and deepgreen modifications exhibit a dimer type of antiferromagnetism (J/cm1=−585 and −565). The hemi adducts with the empirical formula of CuCl2(2-CH2OH·pyo)·1/2L, where L=C2H5OH and H2O, were also isolated. The structural assignments for the three modifications and the two adducts were made on the basis of the similarity of their magnetic and spectral properties to those of dimeric copper(II) pyridine N-oxide complexes, and the whole preparative scheme of these complexes was interpreted in terms of their structural features.
  • Noboru Yoshida, Masatoshi Fujimoto
    1980 Volume 53 Issue 1 Pages 101-105
    Published: 1980
    Released: April 19, 2006
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    The proton-transfer reactions of the univalent anions of 4-(2-pyridylazo)resorcinol (PAR) and 4-(2-hydroxy-5-ethyIphenylazo)benzenesulfonic acid (HEB) with hydroxide ion in dioxane-water media, HA+OH\oversetkf\undersetkr\ ightleftharpoonsA2−+H2O, were studied by means of temperature-jump method. The dependencies of the rate constants, kf and kr on the solvent compositions were interpreted by a mechanism involving the breaking of an intramolecular hydrogen-bond.
  • Osamu Yamauchi, Toshikazu Takaba, Takeshi Sakurai
    1980 Volume 53 Issue 1 Pages 106-111
    Published: 1980
    Released: April 19, 2006
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    Equilibria of histidine-containing ternary amino acid–copper(II) systems have been investigated by potentiometric titration in acid–neutral solution in 20 v/v% dioxane–water containing 0.1 M KNO3 (1 M=1 mol dm−3) at 25 °C. The stability constants of the binary complexes of histidine (his) and other amino acids (A) with a polar or a nonpolar side chain (A: serine, threonine, homoserine, asparagine, glutamine, citrulline, glycine, alanine, or valine) and the ternary complexes Cu(his)(A) have been calculated by the method of nonlinear least-squares. The overall stability constants for CuA, CuA2, and Cu(his)(A) are higher than the values reported for the corresponding complexes in water, those for Cu(his) and Cu(his)2 remaining unaffected. The stability constants (logβ1110) for Cu(his)(A) are in the range 17.4–18.0, no difference in stability being observed between the diastereomers Cu(L-his)(L-A) and Cu(D-his)(L-A). Species distribution as a function of pH reveals that Cu(his)(A) predominates in the neutral region. The stability constants have been compared with various theoretical values and found to be higher than the statistically estimated ones.
  • Tokuji Ikeda, Hideaki Kinoshita, Yoshiyuki Yamane, Mitsugi Senda
    1980 Volume 53 Issue 1 Pages 112-117
    Published: 1980
    Released: April 19, 2006
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    Polarographic behavior of the Brdicka current (catalytic current produced by proteins in ammoniacal buffers containing cobalt ions) of cytochromes c from five sources (horse, chicken, and tuna hearts, C. krusei and S. cerevisiae) and of modified horse cytochromes (metal-substituted, metal-free, and heme-free cytochrome, and carboxymethylated cytochrome at methionyl residues) was investigated at dme and hmde. The results indicate that the heme group and its sixth ligand are important in determining the Brdicka current-activity of cytochromes c. Replacement of the sixth heme ligand from Met to Lys reduced the Brdicka current-activity by about onehalf. Brdicka current of D. vulgaris cytochrome c3 was interpreted as due to four Lys-liganded heme groups.
  • Ryosho Kuwae, Toshio Tanaka
    1980 Volume 53 Issue 1 Pages 118-120
    Published: 1980
    Released: April 19, 2006
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    [Rh(t-BuNC)4]ClO4 undergoes oxidative addition reactions with Ph3SnX (X=Cl, Br) to give cis-[Rh-(Ph3Sn)X(t-BuNC)4]ClO4. The adducts partly dissociate in solution to exist as an equilibrium mixture with the Rh(I) substrate and the addendum. Kinetics of the equilibrium reactions in three different organic solvents were studied spectrophotometrically under pseudo-first-order conditions with excess Ph3SnX. Rate constants for the forward reaction (kf) are strongly dependent on the solvent polarity; kf increases in the order of 1,2-dichloroethane<acetone<acetonitrile, whereas those for the backward reaction are little dependent on the solvents. Activation parameters also were obtained for the X=Cl system in acetonitrile; ΔS\ eweq for the forward reaction is −99.2 J mol−1 K−1, while that for the backward reaction is +24.9 J mol−1 K−1. These results indicate that the addition reactions proceed via a three-center transition state formed by the nucleophilic attack of the Rh(I) ion to the tin atom.
  • Mitsuo Abe, Mitsuo Akimoto
    1980 Volume 53 Issue 1 Pages 121-124
    Published: 1980
    Released: April 19, 2006
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    A study of the distribution coefficients on crystalline antimonic(V) acid (C-SbA) shows an unusual affinity series {Pt(IV)<Au(III)<Pd(II)<<Hg(I), Hg(II), Ag(I)} for microamounts of noble metal ions in nitric acid solution, as compared with ion-exchange resins in strong acid type. Extremely high adsorptive properties are found on the exchange system of Hg(II) and Ag(I), even in relatively high concentrations of nitric acid solution. The ion-exchange studies for macroamounts indicate that a solid solution forms for the system of the Ag(I) ions and hydrogen ions in C-SbA, while two solid phases are presented for the system of Hg(II) ions and hydrogen ions.
  • Masahiro Kuramoto, Yoshihiko Kushi, Hayami Yoneda
    1980 Volume 53 Issue 1 Pages 125-132
    Published: 1980
    Released: April 19, 2006
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    The single crystals of the more-soluble diastereoisomeric salt including the hydrogen-d-tartrate anion as a resolving agent, (−)589-[Co(ox)en2]H-d-tart·2H2O, have been newly obtained, and the crystal structure has been determined by three-dimensional X-ray analysis. The crystals are orthorhombic, space group P21212, Z=4, a=16.583(5), b=14.186(5), and c=7.403(2) Å. The structure was solved by the heavy-atom method and refined by the block-diagonal least-squares method to a conventional R-value of 0.044 for the 1907 independent reflections. One of the two ethylenediamine rings is of the ob form. The other ring has a conformational disorder, the proportion of the ob to the lel form being 50:50. The absolute configuration of the complex cation is denoted as Δ[(50%-δ, 50%-λ)δ]. The framework of the crystal structure is built up of a stack of complex cations and H-d-tart anions along the c-axis in a “head-to-tail” arrangement. The shortest interatomic distance between the H-d-tart anions is 2.473 Å(O–H···O), while that between the complex cations is 2.995 Å (N–H···O). A comparison of the crystal structure of the more-soluble diastereoisomer with that of the lesssoluble one revealed that the {H-d-tart} chain is structurally different from that in the latter; the chain is spiral in the latter, but not in the former. The structural feature in the {H-d-tart} chain is considered to play an important role in the discrimination of the chirality of the [Co(ox)en2]+ cation. The conformational disorder is discussed in connection with the dehydration of crystals.
  • Hiroshi Awano, Hitoshi Watarai, Nobuo Suzuki
    1980 Volume 53 Issue 1 Pages 133-138
    Published: 1980
    Released: April 19, 2006
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    The partition constants Kt\ominus of tris(acetylacetonato)chromium(III) between dodecane and water–organic solvent mixtures have been measured. The organic solvents used as co-solvents were acetonitrile, N,N-dimethylformamide, methanol, ethylene glycol, and dimethyl sulfoxide which are all miscible with water but not with dodecane. From the temperature dependence of Kt\ominus the thermodynamic parameters for the transfer of the complex from dodecane to the mixed solvents have been determined. The dependences of the partition constants on solvent composition of the aqueous phase have been interpreted in terms of changes in the internal pressure and the volume upon mixing of water with the organic co-solvents. The standard transfer enthalpies have been correlated with the excess enthalpies of the mixed solvents.
  • Kiyoshi Isobe, Yukio Nakamura, Shinichi Kawaguchi
    1980 Volume 53 Issue 1 Pages 139-145
    Published: 1980
    Released: April 19, 2006
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    Oxidative addition reactions of 2- and 3-chloropyridines and of 2-chloropyrazine to tetrakis(triphenylphosphine)nickel(0) occurred in toluene at ambient temperature to afford dinuclear nickel(II) complexes containing carbon-bonded heterocycles as a ligand. They are quite stable and the bridging chloride was readily substituted by other halides and pseudohalides preserving the dinuclear structure. 8-Chloroquinoline yielded a mononuclear complex as an exception. These novel organonickel(II) complexes were characterized by analytical and molecular weight data together with IR, 1H NMR, and 13C NMR spectra. Di-μ-chloro-bis(2-pyridyl)bis(triphenylphosphine)dinickel(II) was found to be an excellent catalyst for selective cross coupling of 2-chloropyridine with methylmagnesium bromide.
  • Osamu Itoh, Yoshiro Kohmura, Yasunori Ichikawa, Makoto Umezu, Tsutomu ...
    1980 Volume 53 Issue 1 Pages 146-153
    Published: 1980
    Released: April 19, 2006
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    By the reduction of 1,1-diacylcyclopropanes and their related compounds, several kinds of 1,1-bis(1-hydroxyalkyl)cyclopropanes have been prepared. Some of the stereoisomers were separated, and their configurations were determined by the NMR study of the 1,3-dioxanes prepared by the acetallization of the diols. The diols were subjected to halogenation. Although the reactions of meso- and dl-bis(1-hydroxyethyl)cyclopropanes with thionyl chloride and phosphorus pentachloride gave normal dichlorides, accompanied by slight skeletal rearrangements, the stereospecificities were rather low. With ZnCl2–HCl, the specificities were lost completely and large amounts of the homoallyl derivative were formed. The reaction mechanism is discussed.
  • Haruo Inoue, Tsutomu Shinoda, Mitsuhiko Hida
    1980 Volume 53 Issue 1 Pages 154-159
    Published: 1980
    Released: April 19, 2006
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    The photoamination of 1-amino-2,4-dibromoanthraquinone (1) by butylamine in ethanol was investigated. The reaction was accelerated under an air atmosphere (Φair=1.7×10−3, ΦN2=2.3×104, where [butylamine]=5.00×10−2 mol/dm3). A detailed kinetic study indicated that, under nitrogen, the photoamination proceeded via the T1(3CT) state populated by the intersystem crossing from the S1(1CT) state, while under air it proceeded via both the T1(3CT) and the S1(1CT) states. The latter pathway under air included an interaction between the S1(1CT) state and oxygen to form an exciplex or a collisional complex such as [AQδ+···O2δ−]. The deactivation constant from the T1(3CT) of 1 in ethanol was revealed to be one order of magnitude smaller than that in benzene and one order magnitude larger than that of 1-aminoanthraquinone in benzene. These results were discuessd in relation to the energy diagram in the excited state and the intramolecular heavy-atom effect of bromine in 1.
  • Hiroshi Kosugi, Hisashi Uda
    1980 Volume 53 Issue 1 Pages 160-168
    Published: 1980
    Released: April 19, 2006
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    The synthesis of (±)-dihydrofomannosin acetate [5-acetoxymethyl-1-(4,4-dimethyl-2-oxocyclopentyl)-3-oxabicyclo[4.2.0]oct-5-en-4-one] is described. Photocycloaddition of 4-(2-acetoxy-4,4-dimethylcyclopentyl)-2(5H)-furanone to ethylene gave 5-(2-acetoxy-4,4-dimethylcyclopentyl)-3-oxabicyclo[3.2.0]heptan-2-one, which was converted into ethyl [2-acetoxymethyl-2-(2-acetoxy-4,4-dimethylcyclopentyl)cyclobutyl]glyoxylate by the reaction with 2-methylthio-1,3-dithiane, followed by acetylation and ethanolysis. Introduction of an additional one carbon unit to the glyoxylate was accomplished by the Wittig reaction, and the subsequent hydrolysis and lactonization afforded 1-(2-hydroxy-4,4-dimethylcyclopentyl)-5-methylene-3-oxabicyclo[4.2.0]octan-4-one, which was transformed into 5-acetoxymethyl-5-hydroxy-1-[4,4-dimethyl-2-(tetrahydropyranyloxy)cyclopentyl]-3-oxabicyclo[4.2.0]-octan-4-one. Mesylation followed by elimination and oxidation led to (±)-dihydrofomannosin acetate.
  • Shigeo Hirano, Seiji Takagi, Tamejiro Hiyama, Hitosi Nozaki
    1980 Volume 53 Issue 1 Pages 169-173
    Published: 1980
    Released: April 19, 2006
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    Acid-catalyzed reaction of β,β′-disubstituted cross conjugated dienones or the corresponding ethylene acetals gives mainly 2,3-disubstituted 2-cyclopentenones in stead of the simple Nazarov cyclization products, 3,4-disubstituted 2-cyclopentenones. This transformation is explained in terms of electrocyclic ring-closure, addition of hydroxylic solvent(s), tautomerization of the resulting 2-hydroxycyclopentanone intermediates, followed by solvolysis and isomerization. Based on this working hypothesis a new route to jasmonoids is disclosed which involves acid-treatment of the acyloin disilyl ethers derived from substituted glutarates.
  • Tan Inoue, Teruaki Mukaiyama
    1980 Volume 53 Issue 1 Pages 174-178
    Published: 1980
    Released: April 19, 2006
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    New borylating reagents, (Bu2BOTf and 9-BBNOTf), were prepared in high yields. The triflates reacted with enolizable ketones in the presence of tertiary amines to generate selectively one of the regioisomers of vinyloxyboranes by the choice of the reagents (the dialkylboryl triflates and tertiary amines) under mild reaction conditions. Vinyloxyboranes thus generated showed remarkable reactivity toward aldehydes to give only one regioisomer of the corresponding cross-aldols in good yields. High stereoselectivity was also observed in these reactions.
  • Kazuki Oishi, Kazu Kurosawa
    1980 Volume 53 Issue 1 Pages 179-184
    Published: 1980
    Released: April 19, 2006
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    The oxidation of eight (E)-α-phenylcinnamic acids with manganese(III) acetate in boiling acetic acid containing acetic anhydride gave 3-phenylcoumarins, 3-phenyl-l-oxaspiro[4.5]deca-3,7,9-triene-2,6-diones, 2-phenylbenzofurans, 3-(acetoxymethyl)-2-phenylbenzofurans, 3-formyl-2-phenylbenzofuran, 2-acetoxy-2-phenyl-3 (2H)-benzofuranones, (Z)-α-acetoxystilbenes, 2-acetoxy-1,2-diphenylethanones, 5-acetoxy-4,5-diphenyl-2 (5H)-furanones, and diphenylacetylene. The reaction pathways are discussed.
  • Hiroyasu Nomura, Yoshiaki Tsukamoto, Yutaka Miyahara
    1980 Volume 53 Issue 1 Pages 185-188
    Published: 1980
    Released: April 19, 2006
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    The concentration and temperature dependences of the reorientational correlation times of nitrobenzene in solutions of tetraethyl (TEABr) and tetrabutylammonium bromides(TBuABr) have been determined by Raman line shape analysis. Pure liquid nitrobenzene was evaluated for comparison. The reorientational correlation times of nitrobenzene in solutions decreased with increasing concentration of the salts and the apparent activation enthalpy of τor of nitrobenzene in solutions was larger than in that pure nitrobenzene. From the experimental results, the solution structure of TEABr and TBuABr in nitrobenzene are discussed.
  • Ken-ichi Sato, Masafumi Matsuzawa, Katsumi Ajisaka, Juji Yoshimura
    1980 Volume 53 Issue 1 Pages 189-191
    Published: 1980
    Released: April 19, 2006
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    It was found that 13C NMR spectroscopy is applicable to the unequivocal configurational assignment at the quarternary carbon in seven pairs of 3-C-substituted-hexopyranose derivatives. The configuration of methyl 4,6-O-benzylidene-3-C-nitromethyl-2-O-p-tolylsulfonyl-α-D-glucopyranoside reported by Jordaan et al. is revised to D-allo by a chemical method.
  • Hiroko Aiba, Yasutsugu Shimonishi
    1980 Volume 53 Issue 1 Pages 192-196
    Published: 1980
    Released: April 19, 2006
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    For the synthesis of bovine proinsulin, the S-sulfonate of the A-chain of bovine insulin was elongated by two single-step reactions using Boc–Arg(Tos)–ONSu and Boc–Leu–Glu(OBut)–Gly–Pro–Pro–Gln–Lys[Z(2-Cl)]–N3. The S-sulfonate of the Leu–Glu–Gly–Pro–Pro–Gln–Lys[Z(2-Cl)]–Arg–A-chain, corresponding to positions 53–81 of bovine proinsulin, was obtained after removal of the protecting groups. The S-sulfonates of the elongated derivatives of the A-chain were shown to be very soluble not only in water, but also in organic solvents such as DMF and DMSO in the presence of water. Therefore, these S-sulfonates could react with protected peptides in homogeneous solution. Furthermore, the S-sulfonates could easily be purified by ion-exchange chromatography. The S-sulfonates of the A-chain and its elongated derivatives are thus useful intermediates for the synthesis of proinsulin.
  • Hiroko Aiba, Yasutsugu Shimonishi
    1980 Volume 53 Issue 1 Pages 197-200
    Published: 1980
    Released: April 19, 2006
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    For the synthesis of bovine proinsulin, the S-sulfonate of the Leu–Glu–Gly–Pro–Pro–Gln–Lys[Z(2-Cl)]–Arg–A-chain, which was synthesized using the S-sulfonate of the A-chain of natural bovine insulin and which corresponds to positions 53–81 of bovine proinsulin, was coupled with Boc–Ala–Leu–Glu(OBut)–Leu–Ala–Gly–Gly–Pro–Gly–Ala–Gly–Gly–N3. After removal of the protecting groups from the resulting material the S-sulfonate of the Ala–Leu–Glu–Leu–Ala–Gly–Gly–Pro–Gly–Ala–Gly–Gly–Leu–Glu–Gly–Pro–Pro–Gln–Lys[Z(2-Cl)]–Arg–A-chain, corresponding to positions 41–81 of bovine proinsulin, was purified by chromatography on QAE-Sephadex A-25.
  • Hiroko Aiba, Yasutsugu Shimonishi
    1980 Volume 53 Issue 1 Pages 201-204
    Published: 1980
    Released: April 19, 2006
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    For the synthesis of bovine proinsulin, the S-sulfonate of the Ala–Leu–Glu–Leu–Ala–Gly–Gly–Pro–Gly–Ala–Gly–Gly–Leu–Glu–Gly–Pro–Pro–Gln–Lys[Z(2-Cl)]–Arg–A-chain, which corresponds to positions 41–81 of bovine proinsulin, was coupled with Boc–Arg(Tos)–Arg(Tos)–Glu(OBut)–Val–Glu(OBut)–Gly–Pro–Gln–Val–Gly–N3. The S-sulfonate of the Arg(Tos)–Arg(Tos)–Glu–Val–Glu–Gly–Pro–Gln–Val–Gly–Ala–Leu–Glu–Leu–Ala–Gly–Gly–Pro–Gly–Ala–Gly–Gly–Leu–Glu–Gly–Pro–Pro–Gln–Lys[Z(2-Cl)]–Arg–A-chain, correspoding to positions 31–81 of bovine proinsulin, was obtained in a pure form by removal of the protecting groups from the coupled product and chromatography on QAE-Sephadex A-25.
  • Yoshio Inagaki, Takeo Hosogai, Renji Okazaki, Naoki Inamoto
    1980 Volume 53 Issue 1 Pages 205-209
    Published: 1980
    Released: April 19, 2006
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    2,4-Di-t-butyl-6-methyl-N-(thiosulfinyl)aniline (1) gave 2,4-di-t-butyl-6-methylaniline in the reactions with such reagents as alkylamines, thiourea, butyllithium, alkylmagnesium halides, 1-(1-pyrrolidinyl)cyclopentene, and hydrogen sulfide. Triphenylphosphine reacted with 1 to give (2,4-di-t-butyl-6-methylphenylimino)triphenylphosphorane and bis(2,4-di-t-butyl-6-methylphenyl)sulfur diimide. Reaction of triphenylphosphine with 2,4,6-tri-t-butyl-7,8-dithia-9-azabicyclo[4.3.0]nona-2,4,9-triene afforded 2,4,6-tri-t-butylaniline, bis(2,4,6-tri-t-butylphenyl)sulfur diimide, and 2,4,6-tri-t-butyl-N-sulfinylaniline (7). The sulfur diimide was considered to be formed via intermediary 2,4,6-tri-t-butylthionitrosobenzene, which was trapped by oxygen to give the N-sulfinyl derivative 7.
  • Hiroshi Suginome, Norihisa Yonekura, Tadashi Masamune
    1980 Volume 53 Issue 1 Pages 210-213
    Published: 1980
    Released: April 19, 2006
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    N,O-Diacetyldeoxojervine, obtained by the Wolff-Kishner reduction of jervine followed by acetylation, has been catalytically hydrogenated to (22S,25S)-N,3-O-diacetyl-5α-veratranine-3β,3β-diol. Irradiation in benzene containing mercury(II) oxide and iodine afforded 20-formyl-17β-ethyl-12α-etiojervan-3β-ol 3-acetate which was converted into 17β-ethyl-3β-hydroxy-12α-etiojervan-20-one 3-acetate by dye-sensitized photo-oxygenation of the corresponding morpholine enamine. Reduction to 17β-ethyl-12α-etiojervane-3β,20β-diol 3-acetate with sodium borohydride followed by irradiation in benzene in the presence of mercury(II) oxide and iodine afforded an 18-functional C-nor-D-homosteroid, (20R)-18,20-epoxy-17β-ethyl-12α-etiojervane-3β,20β-diol. The configuration of the methyl group on the tetrahydrofuran ring has been shown to be α on the basis of the NMR spectrum, confirming a previous assignment.
  • Kazuhisa Murata, Akio Matsuda
    1980 Volume 53 Issue 1 Pages 214-218
    Published: 1980
    Released: April 19, 2006
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    Some complexes prepared in situ from Co2(CO)8 and various di(tertiary phosphine)s as ligands have been found to be more active than Co2(CO)8 for the hydroformylation of methyl acrylate. The activity decreased in the order; Ph2P(CH2)2PPh2>Ph2PC≡CPPh2>cis-Ph2PCH=CHPPh2>Ph2P(CH2)3PPh2>none>Ph2PCH2PPh2>Ph2P(CH2)4PPh. The most active catalyst (I) was obtained when a molar ratio of Ph2P(CH2)2PPh2 to Co2(CO)8 was ca. 0.5. The catalyst (I) is also active even at low pressure, where the decomposition of Co2(CO)8 occurs.
  • Akira Sera, Hiroshi Yamada, Kuniaki Itoh
    1980 Volume 53 Issue 1 Pages 219-221
    Published: 1980
    Released: April 19, 2006
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    Irradiation of N,N′-dibronio-2,5-piperazinedione in dichloromethane in the presence of an alcohol induced alkoxybromination of cyclohexene to give trans-1-bromo-2-alkoxycyclohexane in a good yield. The reaction was thought to proceed through an ionic mechanism.
  • Masajiro Kawana, Sakae Emoto
    1980 Volume 53 Issue 1 Pages 222-229
    Published: 1980
    Released: April 19, 2006
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    Two branched-chain deoxy sugars, methyl 5,6-O-cyclohexylidene-3-deoxy-2-C-methyl-β-D-arabino-hexofuranoside and its α-D-ribo isomer, were easily prepared by the one-step reaction of methyl 5,6-O-cyclohexylidene-3-O-mesyl-β-D-allofuranoside (3a) with methylmagnesium iodide. Similarly, the corresponding α-mesylate (4a) gave methyl 5,6-O-cyclohexylidene-3-deoxy-2-C-methyl-α-D-ribo-hexofuranoside. It was demonstrated that these reactions involved 1,2-hydride shifts. The reaction of 3a and 4a with t-butylmagnesium bromide yielded two deoxy sugars, methyl 5,6-O-cyclohexylidene-3-deoxy-β-D-arabino-hexofuranoside and the corresponding α-D-ribo isomer, respectively. Under certain reaction conditions with the Grignard reagents, the sulfonate (3a) afforded dimeric compounds, in which two furanose rings were directly bound with a carbon–carbon bond. A convenient method for the preparation of the sulfonates (3a and 4a) is also reported.
  • Masajiro Kawana, Sakae Emoto
    1980 Volume 53 Issue 1 Pages 230-235
    Published: 1980
    Released: April 19, 2006
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    The selective reaction of acetal protecting groups in sugars with Grignard reagents is described. The treatment of 1,2:5,6-di-O-cyclohexylidene-α-D-glucofuranose (1) with methylmagnesium iodide in benzene-ether at about 85 °C gave 1,2-O-cyclohexylidene-6-O-(1-methylcyclohexyl)-α-D-glucofuranose. When isopropylmagnesium iodide or t-butylmagnesium bromide was used instead of methylmagnesium iodide, 1 gave 1,2-O-cyclohexylidene-6-O-(cyclohex-1-enyl)-α-D-glucofuranose and the corresponding 6-O-cyclohexyl derivative. The selective cleavage of the acetal protecting groups in some other sugars with the Grignard reagents is also described.
  • Morio Yagihara, Yoshio Kitahara, Toyonobu Asao
    1980 Volume 53 Issue 1 Pages 236-238
    Published: 1980
    Released: April 19, 2006
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    The sensitized photooxidation of 7-methoxycycloheptatriene (7-methoxytropilidene) afforded [4+2] cycloadduct (2), tropone, benzaldehyde and their 2-methoxy derivatives. Thermal isomerization of 2 followed by the treatment with alumina yielded 4-methoxytropone. The photooxidation of 1-methoxytropilidene gave 4-hydroxytropone and o-methoxybenzaldehyde, and the photooxidation of 3-methoxytropilidene followed by the treatment with triethylamine afforded 3-methoxytropone, tropone, and o-methoxybenzaldehyde. Characterization of the products and the mechanisms of the reactions are discussed.
  • Yoshito Hanafusa, Masakazu Toda, Yoshio Inoue, Riichiro Chûj&oci ...
    1980 Volume 53 Issue 1 Pages 239-242
    Published: 1980
    Released: April 19, 2006
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    The temperature dependence of carbon-13 chemical shifts has been studied for retinal isomers, N-all-trans-retinylidenebutylamine(all-trans-NRB) and N-all-trans-retinylidenebutylammonium chloride (all-trans-NRB·HCl). The change in the chemical shift was discussed in terms of the temperature dependences of the polarizability and conformation of the polyene-chain. In 11-cis-retinal, the coplanarity between the two parts of polyene-chain separated by the cis bond increases with a lowering of the temperature. The equilibrium between 12-s-cis and 12-s-trans conformers in 11-cis-retinal was studied and it was shown the latter conformer is preferable at low temperatures. In all-trans-NRB and all-trans-NRB·HCl, the temperature dependences of the chemical shifts are similar to those in all-trans-retinal. The extents of the chemical shift changes are in the following order: NRB·HCl<NRB<retinal. This trend can be correlated with the order of the red shifts of the absorption spectra.
  • Akio Murai, Noriaki Iwasa, Masami Takeda, Tadashi Masamune
    1980 Volume 53 Issue 1 Pages 243-253
    Published: 1980
    Released: April 19, 2006
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    17-Oxygenated 12,13-epoxyetiojerv-5-en-3-one 3,3-ethylene acetals (1A10A) were treated with boron trifluoride etherate in benzene at room temperature. The epoxy ring cleavage reactions proceeded slowly with increase of electronegativity of the 17-substituents without and/or with deacetalization to give a variety of compounds including rearranged products (23A and 23B). The results summarized in Table 1 indicated that the reactions produced compounds formed by initial cleavage at less electronegative C-12 rather than at C-13 except several compounds (11A, 20A, 20B, and 34A). Formation of the latter compounds was attributed by hydride shift or neighboring participation of the 17-acetoxyl groups.
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