Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 53 , Issue 3
Showing 1-50 articles out of 63 articles from the selected issue
  • Tsunemichi Okuwa
    1980 Volume 53 Issue 3 Pages 571-573
    Published: 1980
    Released: April 19, 2006
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    The density and the ultrasonic velocity were measured for dioxane–water solutions of sodium chloride at 25 °C. The hydration numbers of sodium chloride were estimated and were compared with those determined by electricalconductivity measurements. The difference between them was discussed. The volume change caused by the dissociation of sodium chloride in a 60 wt % aqueous dioxane solution was determined from the data of the apparent molal volume. This value is in good agreement with that calculated from the excess ultrasonic absorption.
  • Katsumi Niki, Yumiko Takizawa
    1980 Volume 53 Issue 3 Pages 574-576
    Published: 1980
    Released: April 19, 2006
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    The adsorption parameters of butyl alcohol, amyl alcohol, and hexyl alcohol at mercury electrode were evaluated by means of the electrocapillary measurements and compared with those obtained by differential capacity measurements. A marked difference is observed both in the interaction parameters between adsorbed molecules and in the maximum surface excess, Γmax. The inhibition effect by these alcohols on the electrode kinetics of the vanadium(III)/vanadium(II) couple in 0.5 M H2SO4 and of the europium(III)/europium(II) couple in 1.0 M HCl depends only on the surface coverage, θ=Γ⁄Γmax, of the electrode and is independent of the chain length of the adsorbed alcohol. The blocking effect is predominant in the inhibition of the electrode process by these alcohols.
  • Takashi Tamaki
    1980 Volume 53 Issue 3 Pages 577-582
    Published: 1980
    Released: April 19, 2006
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    The steady-state and time-resolved fluorescence spectra were measured for protic solutions of 1- and 2-acetyl- or 1- and 2-benzoylanthracenes at various temperatures. It has been demonstrated that the perturbation of protic solvents on the fluorescence spectra is caused by a combination of the orientational dipolar solvent-solute relaxation and the hydrogen bond interaction. Based on the time-dependent spectral shift and the temperature dependence of fluorescence polarization observed for 2-acylanthracene, the relaxation process of the excited solute has been supposed to involve the level inversion of dual fluorescent states, which respond differently to the solvation of the system.
  • Junzo Sunamoto, Tomiko Hamada, Takafumi Seto, Shinji Yamamoto
    1980 Volume 53 Issue 3 Pages 583-589
    Published: 1980
    Released: April 19, 2006
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    Under the very limited conditions where the mole ratio of water to surfactant is about unity or so, the tightness of the interaction between various ionic surfactants and water solubilized in apolar media was evaluated using the O–H vibrational mode of water in the near infrared spectral region. Water solubilized in apolar solvents containing surfactant exhibited two absorption bands in the region. One of the two arises from water existing in bulk organic phase and appears around 1900–1910 nm. Another band arises from water bound to surfactant and appears over a range of 1920–2020 nm; it is affected primarily by the ionic head group of surfactant rather than by the counter ion. The cationic surfactants were thought to form more rigid micelles than the zwitterionic or anionic ones. The copper (II) ion cosolubilized in the system hardly altered the O–H vibrational energy of water. The dependence of the near infrared absorption band on water, the chemical shift and line width of water proton resonance in NMR, and the fluorescence intensity of terbium chloride all displayed an inflection at the point where the mole ratio of water to surfactant is about unity. This was interpreted in terms of the two step hydration mechanism.
  • Hiroko Mizukoshi, Michiya Itoh
    1980 Volume 53 Issue 3 Pages 590-594
    Published: 1980
    Released: April 19, 2006
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    The interaction of 3,5-dialkyl-4-hydroxybenzylidenemalononitrile (HO-BMN) with ethanol, pyridine, and triethylamine in hexane gives rise to a hydrogen bonding complex formation in a low concentration of ethanol (pyridine and triethylamine) at room temperature. For ethanol concentration >5 mol dm−3, the H-bonded complex exhibits further interaction with another ethanol (pyridine and triethylamine) molecule leading to the formation of anion form of this compound. However, no excited-state proton transfer was observed in several solvents. HO-BMN is fairly fluorescent in a solid solution of boric acid glass at room temperature, as well as in the rigid organic solution at 77 K, but almost non-fluorescent in fluid media at room temperature (φ≈10−4). The non-radiative process of HO-BMN in fluid media is discussed in terms of torsional relaxation of the excited state.
  • Susumu Takamoto
    1980 Volume 53 Issue 3 Pages 595-598
    Published: 1980
    Released: April 19, 2006
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    An extended ligand graph is a set of several points corresponding to donor atoms, where each pair of points is connected by n lines when these atoms are able to form n chelate rings with a metal ion. These graphs can cover all the ligands, but they may not express the geometrical patterns of some complicated ligands clearely enough for them to be discriminated. A complex ligand graph is a set of some main points and sub-points connected by sub-lines, where the main points, sub-points, and sub-lines correspond to donor atoms, carbon atoms forming chelate bonds, and chemical bonds among them respectively. All the complex ligand graphs can then be systematically derived from donor-atomic graphs, which are composed of only main points and main lines and are equivalent to the simple ligand graphs previously designed. Another designing method of ligands is proposed for a certain coordination sturcture. A complex ligand graph to which no more sub-points or sub-lines can be added is called a parent ligand graph. Then all the complex ligand graphs for such a coordination are derived from the parent ligand graphs by neglecting some sub-points or by removing some sub-lines successively.
  • Takahide Saito, Naomichi Iso, Haruo Mizuno, Fumiaki Ozeki, Yoshiyuki M ...
    1980 Volume 53 Issue 3 Pages 599-602
    Published: 1980
    Released: April 19, 2006
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    The monomer molecular weight of phycocyanin was determined by sedimentation equilibrium measurements in 6 mol/1 guanidine hydrochloride (GndCl) and by sodium dodecyl sulfate (SDS)–polyacrylamide gel electrophoresis. The former measurement gave the monomer molecular weight of 4.0×104. From the latter, the phycocyanin was found to be composed of two kinds of subunits, the molecular weights of which were 1.7×104 and 2.0×104. Assumimg that the phycocyanin monomer consists of two polypeptide chains, the molecular weight becomes 3.7×104. These values coincide with the value of 4.2×104 assumed in our previous works, which corresponds to onesixth of the hexamer molecular weight. The sedimentation coefficient, s25w, was 2.21 Svedberg unit, and the intrinsic viscosity in 6 mol/1 GndCl was 19.5 ml/g, at 25.0 °C. From these values, it was clear that the phycocyanin monomer was unfolded in the solvent.
  • Yasushi Iyechika, Kyuya Yakushi, Haruo Kuroda
    1980 Volume 53 Issue 3 Pages 603-610
    Published: 1980
    Released: April 19, 2006
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    The visible and near-infrared reflection spectrum of the single crystal of Wurster’s blue perchlorate was measured at various temperatures over the range of 30–300 K, by using the microspectrophotometric method. The absorption spectra were derived by Kramers-Kronig transformation of the reflection spectra. The intensity ratio of the (0-0) and (0-1) vibronic bands of the local-excitation associated with the π-π* (2B1u2B2g) transition of TMPD+ was found to be anomalous when the spectrum was measured with the light polarized parallel to the b-axis, while not in the spectrum polarized parallel to the a-axis. The Davydov splitting between B3u and B2u components of this absorption band was found to be about 400 cm−1. In the antiferromagnetic (low temperature) phase below 190 K, the charge-transfer band appeared in the a-axis spectrum, showing its absorption maximum at 11.6×103 cm−1, and its intensity increased on lowering the temperature. At the same time, a marked temperature dependence was observed in the local-excitation band. These changes are interpreted in terms of the singlet-triplet model of the dimeric interaction of TMPD+ ions in the low-temperature phase.
  • Keizo Ogino, Nobuo Takeshita
    1980 Volume 53 Issue 3 Pages 611-615
    Published: 1980
    Released: April 19, 2006
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    The solubilization of polar and nonpolar oily materials into an aqueous sodium dodecyl sulfate (SDS) solution with and without sodium chloride was studied. Normal paraffins and their derivatives, with carbon numbers of C7, C8, and C10, were used as solubilizates, the extents of solubilization, the relative viscosities of the solutions, the diffusion coefficients, and the electrophoretic mobilities of the micelles in the solutions were observed, and the effective specific volumes, the effective radii, the ζ-potentials, and the effective charge of the micelles were derived assuming that the micelles were spherical. The micelles of SDS showed increasing mobilities when they incorporated octanoic acid, 1-octanol, and decanoic acid, while the mobilities decreased when they incorporated heptane, octane and 1-decanol. On the basis of these results, we discussed the mechanism of the solubilization of polar and nonpolar oily compounds with SDS.
  • Yasumasa J. I’Haya, Taka-aki Aoi, Tatsuji Sano
    1980 Volume 53 Issue 3 Pages 616-620
    Published: 1980
    Released: April 19, 2006
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    Ultraviolet absorption spectra and induced circular dichroism (ICD) of acridine and phenazine were measured in cellulose diacetate film. The induced Cotton effect corresponding to each absorption maxima of these systems appeared. From the correspondence between the maxima of ICD and the peaks of the resolved absorption spectra, it was found that the sign of ICD is negative in the region where the molecular long-axis polarized transition plays a part in the CD induction and it is positive in the region where short-axis polarized transition does. A mechanism of CD induction tentatively proposed is that a dye molecule is imprisoned in a cage formed by an assembly of the folded chains of cellulose diacetate and the Cotton effect is induced by an electrostatic interaction between electronic transition dipole moments of the dye and of the chromophores involved in the cellulose diacetate cage.
  • Shigeru Koshibe, Yasushi Kai, Noritake Yasuoka, Nobutami Kasai
    1980 Volume 53 Issue 3 Pages 621-626
    Published: 1980
    Released: April 19, 2006
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    The X-ray molecular structure of the photocycloadduct of bicyclo[4.3.0]non-1(6)-en-7-one with 1,4-cyclohexadiene has been determined. The crystals belong to the monoclinic system, space group P21/c, Z=4, a=8.108(1), b=8.836(1), c=7.095(1) Å, and β=95.38(1)° at 22 °C; a=7.975(1), b=8.760(1), c=16.949(2) Å, and β=94.85(1)° at −160 °C. The structure was solved by the direct method and refined by the least-squares procedure to R=0.052 (22 °C) and 0.053 (−160 °C) for 1777 and 2349 non-zero reflections respectively. The ring junction between the four- and six-membered rings is trans. The molecule has the cis-anti-trans structure. No essential difference is observed between the molecular structure at 22 °C and −160 °C except for the thermal motions.
  • Yuji Ohashi, Yoshio Sasada, Seiji Takeuchi, Yoshiaki Ohgo
    1980 Volume 53 Issue 3 Pages 627-634
    Published: 1980
    Released: April 19, 2006
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    The structure of [(R)-1-cyanoethyl][(S)(−)-α-methylbenzylamine]bis(dimethylglyoximato)cobalt(III) has been determined by X-ray analysis at 293 K and 173 K. The crystal is monoclinic; the space group is P21; Z=2, with a=8.665(2), b=13.485(3), c=9.584(3) Å and β=96.95(3)° at 293 K, and a=8.786(2), b=13.500(2), c=9.243(2) Å, and β=98.09(3)° at 173 K. The structures were deduced by the heavy-atom method and refined by the block-diagonal least-squares technique to the final R values of 0.055 and 0.038 for 1940 and 1948 observed reflections at 293 K and 173 K respectively. The bis (dimethylglyoximato)cobalt moiety is twisted around its long axis because of the steric repulsion from the (R)-1-cyanoethyl group and the optically active amine. The degree of the twist is the same as that observed in the structure of [(R)-1-(methoxycarbonyl)ethyl] [(R)(+)-α-methylbenzylamine]bis(dimethylglyoximato)cobalt(III). The conformation of the amine ligand was ascertained to be influenced by the substituted alkyl group through the bis(dimethylglyoximato)cobalt moiety.
  • Hideko Kiriyama, Osamu Nakamura
    1980 Volume 53 Issue 3 Pages 635-641
    Published: 1980
    Released: April 19, 2006
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    The deuteron magnetic resonance spectra of SnCl2·2D2O single crystals have been measured from 208 to 300 K in order to elucidate the static and dynamic structures of water molecules in connection with the phase transition occuring at 234 K. The deuteron quadrupole coupling constants (asymmetry parameters) were determined at 208 K for four non-equivalent water deuterons. These values are 194.2±0.3 (0.066±0.004), 193.2±0.5 (0.112±0.003), 223.3±0.4 (0.206±0.003), and 244.0±0.4 kHz (0.058±0.003), depending largely on the hydrogen-bond strength or the D···O distance. The deuteron arrangements deduced from the EFG tensors agreed well with the ordered structure reported by an earlier ND study. The dynamical process of deuterons responsible for the high-temperature disordered structure was analyzed with the aid of the ND results and was ascribed to a combination of the flip motion of water molecules about each two-fold axis and their rotational motion around each pseudo-three-fold axis.
  • Yoshikazu Kano, Ryuichi Minami, Hiroaki Takahashi
    1980 Volume 53 Issue 3 Pages 642-644
    Published: 1980
    Released: April 19, 2006
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    The dipole relaxation mechanism of carboxylic esters has been studied through the dielectric measurements of seventeen aliphatic esters in cyclohexane solution at 25 °C. The dielectric relaxation times obtained in this experiment are compared with those obtained for a number of rigid molecules under the same conditions. This result indicates that the dipole relaxation process of these esters RC*OOR′ is dominated by intramolecular rotation around the C–C bonds and/or the O–C bond rather than that around the C*–O bond.
  • Masashi Tanaka, Atsushi Watanabe, Jiro Tanaka
    1980 Volume 53 Issue 3 Pages 645-647
    Published: 1980
    Released: April 19, 2006
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    Optical absorption measurements are carried out on pure and BF3 doped polyacetylene films over a wide wavelength region (200 cm−1–54000 cm−1). In the lightly doped polymer, the extra peak appears at 870 cm−1 and it is assigned to the transition from the valence band to the impurity level. This band becomes more intense at low temperature. For the heavily doped films, the dc conductivity of the (CH)x fibril is optically estimated to be σ0=104 Ω−1 cm−1. This value is in good agreement with the calculated value (σ0=0.8×104 Ω−1 cm−1) due to the tight binding model.
  • Makoto Misono, Kanji Sakata, Fumio Ueda, Yasuaki Nozawa, Yukio Yoneda
    1980 Volume 53 Issue 3 Pages 648-652
    Published: 1980
    Released: April 19, 2006
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    Oxidative dehydrogenation of butenes was investigated by use of a flow reactor over three iron oxide catalysts having different structures, i.e., α-Fe2O3, γ-Fe2O3, and Fe3O4, which were prepared in situ by controlled reduction and reoxidation with a pulse method. Under the working conditions of catalytic oxidation, the structures of α- and γ-Fe2O3 remained unchanged, while Fe3O4 was oxidized to γ-Fe2O3, the oxidation state of iron being Fe(III) in all of three iron oxide catalyst. These results are consistent with the kinetics that the reaction was of zeroth order in the partial pressure of oxygen and of nearly first order in the butene partial pressure. γ-Fe2O3, as well as γ-Fe2O3 formed from Fe3O4 under the catalytic conditions, was very active and selective for the reaction, as expected from the results obtained previously with a pulse reactor. It was concluded from the following facts that the oxygen species responsible for this reaction is lattice oxygen of γ-Fe2O3 and that the reaction proceeds by the redox cycles of γ-Fe2O3\ ightleftharpoonsγ-Fe2O3−x. i) Reactivity of γ-iron oxide surface in the stoichiometric oxidation of butenes to butadiene did not change, when the surface oxygen was stepwisely removed by CO-pulses from γ-Fe2O3 to γ-Fe2O2.8. ii) Formation of butadiene from a butene pulse was little affected by whether butenes were pulsed with oxygen or not.
  • Takayuki Ikenaga, Norihiro Matubayasi, Makoto Aratono, Kinsi Motomura, ...
    1980 Volume 53 Issue 3 Pages 653-657
    Published: 1980
    Released: April 19, 2006
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    In order to study the effect of solvent on the adsorption at interfaces, interfacial tension was measured as a function of temperature and compositon for the systems of water and solutions of 1-octadecanol in cyclohexane, cyclohexene, mesitylene, toluene, and benzene. The interfacial density of 1-octadecanol and the entropy and energy of interface formation were calculated thermodynamically. It was found that cyclohexane causes a significant adsorption of 1-octadecanol and marked decreases in the entropy and energy changes, giving rise to phase transition from expanded to condensed film, while benzene, toluene, and mesitylene cause only a slight adsorption and small decrease in thermodynamic quantities. Cyclohexene was found to give rise to an intermediate adsorptive behavior of 1-octadecanol. The results were interpreted in terms of the mutual solubility between water and solvents and that of 1-octadecanol in the solvents.
  • Katsuyoshi Kamakura
    1980 Volume 53 Issue 3 Pages 658-660
    Published: 1980
    Released: April 19, 2006
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    The determination of phenol in water was successfully carried out by means of a new plot of the potentiometric titration data. The plot of the pH vs. the logarithm of the titrant volume gave a titration curve with an inflection between two linear portions, and the center of the inflection obtained by a graphical method was found to correspond to the equivalence point. In the titration of phenol, the data fitted well to the theoretical curve by taking into account the hydrolysis of the phenol ion. The mean of the results obtained from the apparent equivalence point in the concentration range of 1.0–7.7×10−3 mol dm−3 was 101.2% of the results obtained iodometrically after the bromination of phenol, and the precision of the results was ±2.7% (S.D.).
  • Tatsuhiko Tanaka, Kousei Hotta, Takayoshi Yoshimori
    1980 Volume 53 Issue 3 Pages 661-663
    Published: 1980
    Released: April 19, 2006
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    The purity of recrystallized disodium dihydrogen ethylenediaminetetraacetate dihydrate was determined accurately by titration with zinc ion coulometrically generated from an amalgamated zinc anode. The reagents used were of 99.446% ±0.002% homogeneity when the sample was dehydrated and stored in a hygrostat (relative humidity, ca. 58% at 20 °C) over 1 year. Aluminium of high purity (99.99%) was coulometrically titrated with the purified reagent. Aluminium was allowed to react with a certain amount of the reagent, excess of the reagent being titrated with zinc ion anodically generated. The end point was determined potentiometrically using a mercury electrode. The purity was found to be 99.976% with a standard deviation of 0.010% for 6 degree of freedom. Cause of the lower result (0.01%) is discussed.
  • Masato Nishizawa, Kazuo Saito
    1980 Volume 53 Issue 3 Pages 664-667
    Published: 1980
    Released: April 19, 2006
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    Acid hydrolysis of aquaoxo[N-(2-pyridylmethyl)iminodiacetato]vandium(IV) [VO(pmida)H2O], ([H+]=0.1–2.0 M, 1M=1 mol dm−3) and aqua(nitrilotriacetato)oxovanadate(IV) [VO(nta)H2O], ([H+]=0.2–2.0 M) has been studied by the stopped-flow method in aqueous perchloric acid solution at an ionic strength 2.0 (LiClO4). The pseudo first-order rate constant ko is dependent on the proton concentration. The rate formula is expressed by ko=(k1K1[H+]+k2K1K2[H+]2)⁄(1+K1[H+]+K1K2[H+]2). A simulation curve fitting treatment gave the figures: k1=0.02 and 0 s−1, k2=6 and 3000 s−1, K1=1.5 and 0.2 M−1, and K2=0.2 and 0.004 M−1 at 25 °C for [VO(pmida)H2O] and [VO(nta)H2O], respectively. These data indicate that the rate determining step corresponds to the dissociation of the second basal bond of the singly or doubly protonated oxovanadium(IV) complexes.
  • Hiroaki Wada
    1980 Volume 53 Issue 3 Pages 668-672
    Published: 1980
    Released: April 19, 2006
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    An equilibrium study of a part of the Fe–V–S system at sections with atomic Fe: V ratios of 1:0, 9:1, and 4:1 was carried out by means of thermogravimetry. The thermochemical data which were obtained in the range of log(PS2/atm)=−4 to −0.8 at temperatures between 520 and 814 °C are presented. The compositional limits of the univariant assemblage of Fe1−δS–FeS2–(Fe,V)3S4 were determined at 570 °C on the basis of X-ray analyses of the quenched specimens. The rate of FeS2 formation under the experimental conditions employed was studied qualitatively from the point of view of the sulfidation kinetics of iron vanadium sulfides.
  • Sanshiro Komiya, Shoshiro Tane-ichi, Akio Yamamoto, Takakazu Yamamoto
    1980 Volume 53 Issue 3 Pages 673-679
    Published: 1980
    Released: April 19, 2006
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    A series of bis(aryloxo)iron(II), 2a2g, and bis(alkoxo)iron(II), 2h2k, complexes with 2,2′-bipyridine ligands (Fe(OC6H4X)2(bpy)n and Fe(OR)2(bpy)n) have been prepared by the reactions of diethylbis(2,2′-bipyridine)iron(II) (1) with corresponding p-substituted phenols and alcohols, respectively. (X=NO2, CN, Cl, C6H5, H, and CH3; R=CH3, C2H5, iso-C3H7, and CH2C6H5). These compounds were characterized by IR and NMR spectroscopies and elemental analyses as well as by chemical reactions. Kinetic investigation of the reactions of 1 with phenols by a visible spectroscopic method supports a mechanism involving partial dissociation of the 2,2′-bipyridine ligand, followed by coordination of phenol and activation of the Fe–C2H5 bonds giving the bis(phenoxo)iron(II) compound. Thermolysis of bis(alkoxo)iron(II) complexes gives not only disproportionation products of the alkoxo ligands (alcohols and aldehydes) but also organic products which are obtained as the result of C–O bond cleavage of the alkoxo groups. Interactions of 2 with acyl and alkyl halides lead to the formation of corresponding esters and ethers. Reactions of these iron(II) complexes with various organic acetates give corresponding acetates via an alkoxo exchange reaction. Bis(aryloxo)iron(II) complexes, 2, are hydrolyzed with H2O to yield phenols. Catalytic trans-esteriflcation between ester and alcohol and Tishchenko type dimerization of benzaldehyde are effectively promoted under mild conditions by the bis(phenoxo)iron(II) and bis(benzyloxo)iron(II) complexes, respectively.
  • Takakazu Yamamoto, Minoru Kubota, Akio Yamamoto
    1980 Volume 53 Issue 3 Pages 680-685
    Published: 1980
    Released: April 19, 2006
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    Carbon dioxide reacts with ROCu(PPh3)2 (R=C2H5, C6H5CH2; PPh3=triphenylphosphine) to produce ROCO2Cu(PPh3)2. Hydrolysis or thermolysis of the alkylcarbonatocopper(I) complexes gives a binuclear carbonatocopper(I) complex (PPh3)2CuOCO2Cu(PPh3)2, which is further converted into a hydrogencarbonatocopper(I) complex [HOCO2Cu(PPh3)2]n by the reaction with CO2 in moist solvents. The IR spectrum of [HOCO2Cu(PPh3)2]n shows association of the HOCO2Cu(PPh3)2 units through hydrogen bonds. The IR spectrum of [HOCO2Cu(PPh3)2]n also reveals that the mode of the association depends on conditions of the crystallization of the complex. The reaction of (PPh3)2CuOCO2Cu(PPh3)2 with CH3I gives (CH3O)2CO and the reaction of [HOCO2Cu(PPh3)2]n with C6H5NH2 affords C6H5NHCO2Cu(PPh3)2 in high yields. Carbon dioxide reacts also with an amidocopper(I) complex C6H5NHCu(PPh3)2 to yield a carbamatocopper(I) complex C6H5NHCO2Cu(PPh3)2. The reaction of CH3Cu(PPh3)2(diethyl ether)0.5 with CO2 in the presence of HN(C2H5)2 affords (C2H5)2NHCO2Cu(PPh3)2. The isocyanate group of phenyl isocyanate is inserted into the C2H5O–Cu bond of C2H5OCu(PPh3)2 to give a (ethyl N-phenylcarbamato)copper complex.
  • Tokuji Ikeda, Yoshiyuki Yamane, Hideaki Kinoshita, Mitsugi Senda
    1980 Volume 53 Issue 3 Pages 686-690
    Published: 1980
    Released: April 19, 2006
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    Effect of pH and buffer concentrations on Brdicka currents produced by horse heart cytochrome c was investigated in the presence of hexaamminecobalt(III) chloride in ammonia, tris(hydroxymethyl)aminomethane, N,N-dimethylglycine, borate, and carbonate buffer solutions at pH varying between 8.2 and 10.7. The Brdicka current-activity of the protein varied with pH and the kind and concentration of buffers, but, if corrected for the effect of the buffer salts, showed a sigmoidal pH-dependence. The pH-dependence was interpreted as due to the protonic dissociation of Lys-79 of the protein. Brdicka currents of the protein were observed also in unbuffered solutions containing no proton donor except water. The current intensity was explained by taking into account the change of pH at electrode surface. The results indicate that a main proton donor in the Brdicka reaction is a water molecule.
  • Motowo Yamaguchi, Shigenobu Yano, Masahiko Saburi, Sadao Yoshikawa
    1980 Volume 53 Issue 3 Pages 691-698
    Published: 1980
    Released: April 19, 2006
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    The preparation and structural assignments of N-methyl-(S)- and -(R)-alaninatocobalt(III) complexes with a few chiral derivatives of 2,3,2-tet (=3,7-diazanonane-1,9-diamine) and triethylenetetramine are described. The hydroxide ion-catalyzed epimerizations of these complexes are examined at pH 10. In the N-methylalaninato complexes the isomer ratio for Λ-S/Λ-R ranged from 76/24 to 90/10. In the most favorable case where tetramine is 2(S)10(S)-4,8-diazaundecane-2,10-diamine (abbreviated as 2(S)10(S)-Me2-2,3,2-tet) the energy differences among the four possible diastereomers are discussed in relation to the prediction from strain energy minimization calculations.
  • Koji Takeuchi, Kunio Ohzeki, Tomihito Kambara
    1980 Volume 53 Issue 3 Pages 699-702
    Published: 1980
    Released: April 19, 2006
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    The effects of column outlet pressures on the HETP vs. carrier gas velocity curves are discussed on the basis of KOS theory. It is shown that when a column is operated at a constant outlet pressure higher than atmospheric the minimum of H-\baru curve shifts towards lower HETP and \baru values, and on the contrary the operation at reduced outlet pressure results in the shift of the minimum towards higher HETP and \baru values. The separation factor and number of theoretical plates obtained by a column operated at the outlet pressure of 4.0 atm are superior by ca. 10% to those obtained by normal gas chromatography.
  • Tadashi Iwachido, Masayosi Minami, Masaho Kimura, Akira Sadakane, Miki ...
    1980 Volume 53 Issue 3 Pages 703-708
    Published: 1980
    Released: April 19, 2006
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    Alkali and alkaline earth metal salts of 2,2′,4,4′,6,6′-hexanitrodiphenylamine (HND) were extracted into nitrobenzene in the absence or presence of several crown ethers or cryptands which differ from one another in hole size. The quantity of water transferred to the nitrobenzene phase was determined by means of the Karl-Fischer method. The NMR and near-infrared spectra show that the coextraction of water is caused by the hydration of the cations. The number of water molecules attached to the cations increases upon going from Cs+ (0.6) to Li+ (5.6) and from Ba2+ (10.5) to Ca2+ (13.0). The complexation between these cations and the crown ethers causes a clear decrease in the hydration number; e.g., in the 1:1 metal–crown ether complexes, more than half of the water molecules are removed, and in the 1:1 metal–cryptand complexes, less than one water molecule remains unremoved. The complexes of a 1:2 stoichiometry are also found; some are stable and carry virtually no water molecules. The number and type of donor atoms have no significant effect on the coextraction of water. The presence of fused benzo rings on the crown ether also has no influence on the number of water molecules.
  • Tohru Shibata, Takashi Tsuji, Shinya Nishida
    1980 Volume 53 Issue 3 Pages 709-716
    Published: 1980
    Released: April 19, 2006
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    The cycloadditions of dispiro[2.2.2.2]deca-4,9-diene (1) to isolated carbon-carbon multiple bonds have proceeded in two different modes, giving dispiro[2.2.4.2]dodeca-4,11-diene and tricyclo[6.4.0.03,6]dodeca-2,7-diene derivatives. Mono- and 1,2-disubstituted olefins and acetylenes gave the former adducts, whereas 1,1-disubstituted olefins gave the latter, as the major products. Evidence for the intermediacy of biradicals is provided. The observed difference in the mode of the cycloaddition is explained in terms of the stereoelectronic and/or steric effects in the transition state for the cyclization of the intermediate. The addition of 1 to tetracyanoethylene (TCNE) in wet acetone has proceeded via a zwitterionic intermediate(s), giving a 1:1:1 adduct of 1, TCNE, and water.
  • Minoru Hirota, Toshiyuki Sekiya, Akira Hishikura, Hiroko Endo, Yoshiki ...
    1980 Volume 53 Issue 3 Pages 717-719
    Published: 1980
    Released: April 19, 2006
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    The tautomeric behavior of 5-nitro-2-anilinopyridine and 2-anilinopyrimidine was studied. 2-(N-Methylanilino) and l-methyl-2-(phenylimino)-1,2-dihydro derivatives were prepared as models for the amino and imino tautomers, respectively, and their spectra were compared. The results and the assumed tautomeric equilibrium constants strongly suggest the equilibria to be favorable to the amino tautomers, the Kt values being considerably smaller than that of the parent 2-anilinopyridine.
  • Yozo Miura, Hidetsugu Asada, Masayoshi Kinoshita
    1980 Volume 53 Issue 3 Pages 720-725
    Published: 1980
    Released: April 19, 2006
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    A series of N-(alkylthio)arylaminyls, ArNSR, were generated by hydrogen-abstraction from N-(alkylthio)anilines or by the photolysis of N,N-bis(t-butylthio)anilines, and were studied by ESR spectroscopy. N-(t-Butylthio)aminyls were fairly long-lived, and their lifetimes were scarcely affected by oxygen. Substituent effects on the ESR parameters were also studied, and the results were compared with those for N-alkoxyarylaminyls.
  • Takumi Oshima, Toshikazu Nagai
    1980 Volume 53 Issue 3 Pages 726-730
    Published: 1980
    Released: April 19, 2006
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    The reactions of several aryldiazomethanes (1a: p-tolyl; 1b: phenyl; 1c: p-chlorophenyl) with chloranil gave stilbenes (3) and spiro-oxetanes (4) at 20 °C in tetrahydrofuran or 1,2-dichloroethane. The isomer ratios of 3 were ca. 2 to 3:1 in favor of cis, depending on the solvents and on the substituents of 1. In the case of 4, however, stable trans-isomers were selectively formed. On the other hand, the presence of added CH3OH suppressed the formations of 3 and 4 and, instead, induced redox reactions giving α,α-dimethoxyarylmethanes and tetrachlorohydroquinone (6). In these redox reactions, the acid decompositions of 1 with 6 were also found. However, the presence of CF3CH2OH allowed the formation of considerable amount of 3 and 4, along with the redox products. The mechanism of these reactions will be discussed.
  • Shiro Hatakeyama, Tsutomu Mitsuhashi, Michinori Oki
    1980 Volume 53 Issue 3 Pages 731-735
    Published: 1980
    Released: April 19, 2006
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    The bromination of 9-allyl-1,2,3,4-tetrachlorotriptycene affords a mixture of bromoolefins together with a minor quantity of the corresponding dibromide. By the examination of the reactions of model compounds, it is concluded that the first attack of bromine on the olefinic bond takes place in the meso rotamer and the resulted bromonium ion collapses either by attack of the tribromide ion to produce the dibromide or by internal rotation about the C9–Callyl bond followed by attack of the tribromide ion to produce the bromoolefin. Examination of the bromoolefin/dibromide ratios at various temperatures suggests that the activation energy for the attack of the tribromide ion on the bromonium ion is ca. 3 kcal/mol higher than the rotational barrier.
  • Junzo Yamashita, Shinji Ishikawa, Harukichi Hashimoto
    1980 Volume 53 Issue 3 Pages 736-739
    Published: 1980
    Released: April 19, 2006
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    Base-catalyzed autoxidation of fluorene to fluorenone has been carried out in an aqueous potassium hydroxide–benzene two-phase system in the presence of 18-crown-6 as a phase transfer catalyst. The initial rate of oxidation is proportional to the amount of fluorene. The addition of 18-crown-6 leads to the increased concentration of potassium hydroxide and water in the benzene phase, which is responsible for the increased rate of oxidation. Increasing the concentration of potassium hydroxide in the aqueous phase increases the concentration of 18-crown-6 and potassium hydroxide in benzene, resulting in a large increase in the rate of oxidation. The ease of oxidation with respect to the base is KOH>NaOH>LiOH>Ba(OH)2. Less polar solvents such as cyclohexane used as an organic phase decrease the oxidation rate.
  • Yumihiko Yano, Yoshiharu Tamura, Waichiro Tagaki
    1980 Volume 53 Issue 3 Pages 740-744
    Published: 1980
    Released: April 19, 2006
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    The rates of benzoin condensation catalyzed by thiazolium salts of varying structures have been determined in methanol containing triethylamine as the base by the method of gas chromatography. The condensation activity was observed not to be linearly correlated with the acidities of 2-position of catalyst thiazolium ring. The dimethylamino substituent was found not to act as an internal base for benzoin condensation, but rather exerted an inhibitory effect. In general, the effects of N-substituent on the rate of benzoin condensation were small. However, a large steric hindrance was observed for 3-methyl-4-menthylthiazolium perchlorate.
  • Kimiaki Imafuku, Kazuko Yamaguchi, Hisashi Matsumura
    1980 Volume 53 Issue 3 Pages 745-747
    Published: 1980
    Released: April 19, 2006
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    3-(1-Phenylvinyl)tropolone (3b) was prepared by the hydrolysis of cycloadducts of 6-methyl-6-phenylfulvene with dichloroketene. 3-Isopropenyltropolone and 3b were treated with 2,3-dichloro-5,6-dicyano-p-benzoquinone or performic acid to give 3-methyl- and 3-phenyl-8H-cyclohepta[b]furan-8-one, respectively. Reaction of 3b with hydrazoic acid afforded an unexpected 3-acetyltropolone.
  • Tatsuro Ouchi, Noriyuki Murayama, Minoru Imoto
    1980 Volume 53 Issue 3 Pages 748-752
    Published: 1980
    Released: April 19, 2006
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    The homogeneous polymerization of methyl methacrylate (MMA) initiated with butanal (PrCHO), pentanal (BuCHO), and hexanal (C5H11CHO) was carried out in dioxane. It was found that the rate of polymerization can be expressed by Rp=k[MMA]1.5[RCHO]0.5. The polymerization was confirmed to proceed through a radical mechanism. Overall activation energies, when PrCHO, BuCHO, and C5H11CHO were used, were estimated to be 37.2, 36.3, and 36.0 kJ mol−1, respectively. Instead of MMA, many kinds of vinyl monomer were applied. Various methacrylates and acrylates could be polymerized, but not styrene and acrylonitrile. The effect of solvent on the rate of polymerization was studied.
  • Hideo Tomioka, Takaaki Miwa, Shinji Suzuki, Yasuji Izawa
    1980 Volume 53 Issue 3 Pages 753-756
    Published: 1980
    Released: April 19, 2006
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    Carbene processes within the t-BuOH matrix at −196 °C were investigated in order to show the utility of the matrix as a tool for the study of carbene chemistry. The photolysis of several aryldiazomethane derivatives in the t-BuOH matrix gave the olefinic dimer as the main product, probably arising from a combination of two triplet arylcarbenes in the aggregate of molecules. The similar photolysis of other diazo compounds (e.g., N2CHCOR, R=OR′, NEt2, and Ph) resulted in no detection of the olefinic dimer. This was explained in terms of the structural effect on the ground-state multiplicity of carbene. The photolysis of Ph2CN2 in t-BuOH containing 5% EtOH at −196 °C gave almost exclusively O–H and C–H insertion products with the solute alcohol at the expense of the O–H insertion product with the host, i.e., Ph2CHOBut, which was the major product in the liquidphase photolysis. This is ascribable to the co-aggregation of the carbene precursor with the solute alcohol because of the relatively large guest hole provided by the bulky tertiary alcohol matrix. A more general utility of this matrix was shown in the reaction of Ph2C with Ph2CO to give oxirane, in which the intervention of carbonyl ylide was demonstrated at low temperatures.
  • Kazuhiro Maruyama, Noritsugu Narita
    1980 Volume 53 Issue 3 Pages 757-763
    Published: 1980
    Released: April 19, 2006
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    Photolysis of a benzene solution of 2-alkyl- or 2,3-dialkyl-substituted 1,4-naphthoquinone mixed with an arylsubstituted ethylene afforded 3,4-benzobicyclo[4.2.0]octene-2,5-dione derivatives (cyclobutane type adducts) in a good yield without any other types of products. The orientation of the cycloaddition was likely to control by the adverse van der Waals repulsion of the substituents of the quinone and olefin in addition to the electronic effects of the substituents. The predominant factor orientating the cycloaddition seems to play the van der Waals repulsion due to the substituents both of quinone and olefin.
  • Hiroshi Kimoto, Kensuke Takahashi, Hiroshige Muramatsu
    1980 Volume 53 Issue 3 Pages 764-769
    Published: 1980
    Released: April 19, 2006
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    Benzophenone photo-sensitized addition of indene to chlorofluoroethylenes [trichlorofluoroethylene, 1,2-dichloro-1,2-difluoroethylene, 1,1-dichloro-2,2-difluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene] afforded 6,6,7,7-tetrahalogeno-2,3-benzobicyclo[3.2.0]hept-2-enes as corresponding cycloadducts. The structure of the cycloadducts obtained from unsymmetrical chlorofluoroethylenes shows that the addition reaction proceeds with good regioselectivity. Some reactions such as oxidation, reduction, dechlorination, and halogenation of the cycloadducts were also examined.
  • Sotaro Miyano, Hiroshi Hokari, Yoshiharu Umeda, Harukichi Hashimoto
    1980 Volume 53 Issue 3 Pages 770-774
    Published: 1980
    Released: April 19, 2006
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    Terminal alkenes, R–CH=CH2 (R=Et, n-Pr, n-Bu, n-Hex), were readily transformed into 1-chloro-3-iodoalkanes by the AIBN-induced free radical addition of chloroiodomethane. Thus, 1-chloro-3-iodoheptane was obtained from 1-hexene in an 88% yield; this in turn was allowed to react with dialkyl malonates in the presence of alkoxides in alcohols to give dialkyl 2-butylcyclobutane-1,1-dicarboxylates and dialkyl (E)-3-octene-1,1-dicarboxylates (7), either of which could be obtained preferentially by the choice of the experimental parameters. The olefinic product, 7, was further utilized for the synthesis of (E)-5-decenyl acetate and/or 1,4-nonanolide.
  • Shigeru Oae, K\={o}ichi Shinhama, Ken Fujimori, Yong Hae Kim
    1980 Volume 53 Issue 3 Pages 775-784
    Published: 1980
    Released: April 19, 2006
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    Several new sulfonyl or sulfonyl derivativives, thionitrates (RSNO2), sulfonyl nitrites (RSO2NO), were successfully isolated by treating corresponding thiols and sulfinic acids with dinitrogen tetraoxide (N2O4). Spectroscopic data of both stable and many rather unstable compounds were determined and compared with those of corresponding alkyl nitrites (RONO) or alkyl nitrates (RONO2). Chemical reactivities of these uncommon, novel S-nitroso and S-nitro compounds were investigated.
  • Hiroshi Hirota, Yoshiaki Tanahashi, Takeyoshi Takahashi
    1980 Volume 53 Issue 3 Pages 785-788
    Published: 1980
    Released: April 19, 2006
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    The structure including absolute stereochemistry of “LB”, one of the volatile constituents of “San-shion” (the roots of Ligularia species), was found to be (1S,4R,5S,7R,10R)-5,11-epoxyguaiane.
  • Daiyo Terunuma, Katsutoshi Murakami, Masanori Kokubo, Kazuhisa Senda, ...
    1980 Volume 53 Issue 3 Pages 789-794
    Published: 1980
    Released: April 19, 2006
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    New optically active α-amino organosilanes, such as benzylmethylphenylsilylmethylamine, benzylmethyltolylsilylmethylamines, and anisylbenzylmethylsilylmethylamines, were obtained by the fractional crystallization of the salts of the amines and (+)-tartaric acid. Benzylmethylphenylsilylmethylamine was converted into benzylmethyl-1-naphthylphenylsilane, of which the configuration had been known. From these observations, it was found that benzylmethylphenylsilylmethylamine, benzylmethylphenylsilane, and benzylmethoxymethylphenylsilane had S(+), S(−), and S(+) configurations respectively.
  • Toshihiro Tominaga, Theodore B. Stem, Jr., D. Fennell Evans
    1980 Volume 53 Issue 3 Pages 795-799
    Published: 1980
    Released: April 19, 2006
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    Conductance, viscosity, and EMF measurements were used to characterize solutions containing surfactant-alcohol micelles. The materials studied included sodium dodecyl sulfate (SDS), sodium octyl sulfate (SOS), decyltrimethylammonium bromide (DTAB), hexadecyltrimethylammonium bromide (CTAB) and the alcohols 1-pentanol through 1-octanol. The addition of alcohols caused the conductance of a 2% SDS solution to increase, and of a 3% solution of DTAB and of a 7% solution of SOS to decrease. CTAB showed both increases and decreases upon addition of alcohol. The EMF measurements permitted the concentration of free surfactant monomer and of unbound counterion in equilibrium with the micelle to be determined. When combined with the viscosity data, the change in conductance upon addition of alcohol can be interpreted in terms of changes in micellar shape and in the concentration of involved ions.
  • Hiroshi Fujimoto, Takashi Yokoyama
    1980 Volume 53 Issue 3 Pages 800
    Published: 1980
    Released: April 19, 2006
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    A valence structural analysis of S2N2 has been performed within the framework of the INDO approximation. The fractional double-bond character has been suggested to be the consequence of the interaction between nonionic and ionic structures, counterbalanced in part by the overlap repulsions in the ring.
  • Taiichi Hayashi, Kazuaki Nakata, Yoshito Takaki, Kiichi Sakurai
    1980 Volume 53 Issue 3 Pages 801-802
    Published: 1980
    Released: April 19, 2006
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    The crystal of the title compound is monoclinic with space group P21/a, a=9.11, b=9.54, c=8.18 Å, β=93.8°, Z=4. The structure was solved by a packing analysis based on an ellipsoid-model and refined by block-diagonal least-squares calculations to R=0.115. The amide group makes a dihedral angle of 2.0° with the benzene ring.
  • Tomohiko Taniguchi, Yoshito Takaki, Kiichi Sakurai
    1980 Volume 53 Issue 3 Pages 803-804
    Published: 1980
    Released: April 19, 2006
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    The crystal structures of the α and β forms of DL-methionine have been refined by block-diagonal least-squares calculations using three-dimensional X-ray data to R=0.118 and 0.088 respectively. The structures of both the forms are essentially the same as those previously reported by Mathieson (Acta Crystallogr., 5, 332 (1952)).
  • Emiko Ohyoshi, Akira Ohyoshi
    1980 Volume 53 Issue 3 Pages 805-806
    Published: 1980
    Released: April 19, 2006
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    The tartrate complexes of Ce(III) and Tm(III) were studied by the cation-exchange method, where a series of solutions prepared so as to keep the [Htart] value nearly constant, while the [tart2−] value was varied, was used for the estimation of the protonated complexes. Three kinds of complexes, M(Htart)2+, M(Htart)(tart), and M(tart)2, were found in the lower pH region of the solutions.
  • Susumu Kohata, Hitoshi Kawaguchi, Noriko Itoh, Akira Ohyoshi
    1980 Volume 53 Issue 3 Pages 807-808
    Published: 1980
    Released: April 19, 2006
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    The isothermal kinetics of the substitution reaction of an ammonia with an outer-sphere anion was studied in the solid state; [RhX(NH3)5]X2(s)→[RhX2(NH3)4]X(s)+NH3(g) (X=Cl, Br, I). The kinetic parameters provided some evidence for a dissociative mechanism.
  • Yoshinori Yamamoto, Kunio Shibahara, Shinsuke Takei
    1980 Volume 53 Issue 3 Pages 809-810
    Published: 1980
    Released: April 19, 2006
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    The title nickel chelate, which has a planar four-coordinated form, gave an intense new band, no corresponding band of which was observed with the other chelates, at the position between the first and second π-π* bands. The spectra were compared with those of the corresponding compounds free from the acetyl group.
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