Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 59 , Issue 3
Showing 1-50 articles out of 55 articles from the selected issue
  • Masamichi Akimoto, Hirotoshi Suto, Hiroo Niiyama
    1986 Volume 59 Issue 3 Pages 683-687
    Published: 1986
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The vapor-phase catalytic decomposition of COS (COS→CO+1/xSx and 2COS→CO2+CS2) has been mechanistically investigated so as to prepare solid catalysts which are active and selective for the first reaction. The comparison of the catalytic activity and selectivity of a series of Al2O3 catalysts with their acid-base properties and the different behavior of these two catalytic decomposition reactions in the poisoning of an Al2O3 catalyst with SO2 demonstrate that electron-donating sites catalyze the first reaction whereas Lewis acidic sites do so the second reaction. CaO catalysts are prepared by thermal decomposition of CaCO3 at elevated temperatures and their catalytic activity is compared with their amount of electron-donating sites. The greatest catalytic activity and selectivity for the first reaction(yield of CO+Sx=21.4%, selectivity=80.2% at 873 K) are obtained over CaO catalyst prepared at 1123 K which has the greatest electron-donating ability. These values of the yield and selectivity to CO+Sx are much greater than those obtained over Al2O3 catalysts.
  • Masahiro Orita, Isao Kojima, Eizo Miyazaki
    1986 Volume 59 Issue 3 Pages 689-695
    Published: 1986
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The catalytic decomposition of methanol was investigated on a series of powdered transition-metal carbides, such as TiC, TaC, Mo2C, WC, and W2C, which had been catalytically activated by evacuation at high temperatures. WC was found to produce methyl formate (HCOOCH3) with a high selectivity (above 80%), whereas CO and H2 were mainly produced on clean TaC, Mo2C, and W2C surfaces. XPS measurements combined with an analysis of the peak intensities revealed that the catalytic activation of WC and TaC was attributable to the removal of surface oxygen and the subsequent formation of monocarbide surfaces. On the other hand, the minor activities leading to the formation of methyl formate on W2C and Mo2C were concluded to be due to the formation of oxycarbide surfaces. The deuterium distributions in the products during the reaction of CH3OD suggest that the methyl formate is produced via the dimerization of the intermediate adspecies, CH2O.
  • Kunio Esumi, Kazuki Yamada, Toshie Sugawara, Kenjiro Meguro
    1986 Volume 59 Issue 3 Pages 697-701
    Published: 1986
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The interactions of disodium salt of bis(3-sulfopropyl) α,ω-alkanedicarboxylate(C10-α,ω and C12-α,ω) with monodispersed spherical particles of iron(III) oxide hydrate sols were studied by measuring the mean particle size, the zeta-potential and the amounts of adsorption. The sols were flocculated by the addition of small amounts of C10-α,ω and C12-α,ω. The flocks thus formed were redispersed by the further addition of these surfactants. The flocculation of sols upon the addition of α,ω-type surfactants occurred over a wider concentration range than upon the addition of an ordinary surfactant, such as sodium dodecyl sulfate(SDS). Furthermore, the mechanism of redispersion upon the addition of α,ω-type surfactants is different with the two fold adsorption layer in SDS.
  • Kenji Ishikawa, Shin-ichi Kondo, Yuichi Suzuki, Shin-ichi Takayama, Ka ...
    1986 Volume 59 Issue 3 Pages 703-706
    Published: 1986
    Released: June 27, 2006
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    The electrical resistivities and Seebeck coefficients of mixed oxides, La2−xSrxNiO4, have been determined under an He atmosphere at 77.4–673.2 K. It has been shown that the temperature dependences of the Seebeck coefficients of the oxides were fairly well approximated by this equation: S=AT+B+CT, where T is the thermodynamic temperature. The coefficients of the equation, A, B, and C, were given by the least-squares method. The metal-semiconductor ratios {α≡(CT)⁄(AT+CT)} were given to characterize the thermoelectrical properties of La2−xSrxNiO4. The maximal activation energies (Ea(resis.) and Ea(Seebeck)) and the maximal metal-semiconductor ratio (α) were obtained with the strontium concentration of La2−xSrxNiO4 at x=0.5. The lattice distortion of the oxides is responsible for the maxima of the activation energies and of the metal-semiconductor ratio at x=0.5.
  • Shigeo Kato, Hiroyasu Nomura, Ryszard Zielinski, Shoichi Ikeda
    1986 Volume 59 Issue 3 Pages 707-713
    Published: 1986
    Released: June 27, 2006
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    A cylindrical resonator for the measurement of ultrasonic absorption has been designed. It was found that a newly designed resonator can determine the absolute value of the ultrasonic absorption coefficient of water at frequencies above 0.7 MHz. For aqueous solutions it has a sufficient resolution power down to 0.2 MHz by means of a reference measurement. Precise measurements of ultrasonic absorption were carried out for aqueous solutions of dodecyltrimethylammonium bromide using a newly designed resonator and two other previously reported resonators. The ultrasonic relaxation spectra show a single relaxation process within the investigated frequency range. The relaxation process can be ascribed to a “fast” relaxation related to the exchange of a surfactant between micelles and bulk solution. The kinetic parameters for the exchange process were estimated on the basis of Teubner’s theory.
  • Yoshifumi Koide, Shigekazu Sato, Kimiho Yamada
    1986 Volume 59 Issue 3 Pages 715-720
    Published: 1986
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Colored surfactants containing complex radicals(R-Bc, R-Bs, R-Sh, R-S, R-C, R-Ha, and R-Hb) were applied as ion-flotation collectors and foam-fractionation collectors. The extent of floatabilities for the colored complexing surfactants and metal ions was easily recognized by the degree of discoloration. R-Bc, R-Bs, and R-Sh with low HLB values formed floatable complexes in pH 6–9 with Cu2+, Cd2+, Hg2+, Pb2+, and Sr2+. The residual concentrations of R-Sh, R-Bc, and R-Bs were below 0.1 ppm; however, these concentrations gradually increased after obtaining a minimum concentration of metal ions. Since R-C, R-Ha, and R-Hb had high HLB values, they easily floated Cu2+, Pb2+, and Cd2+ by foam fractionation. The concentrations of R-C, R-Ha, and R-Hb in foams or aqueous solutions were correlated to their foaming abilities.
  • Hideo Horii, Yasuo Abe, Setsuo Taniguchi
    1986 Volume 59 Issue 3 Pages 721-724
    Published: 1986
    Released: June 27, 2006
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    The reaction between the hydroxyl radical (OH) and triose reductone (2,3-dihydroxy-2-propenal) in an aqueous solution has been studied by spectrophotometric pulse radiolysis. The OH radical adds to triose reductone (TRH2) to form the transient OH adduct (TRH(OH)−·) with an absorption maximum at 398 nm, ε=3150 M−1 cm−1 (1 M=1 mol dm−3) in a neutral solution. The OH adduct decays by second-order kinetics in the pH range 2–12. The rate constants for the reactions of the OH radical with dissociated and undissociated triose reductone are 1.4×1010 M−1 s−1 and 9.9×109 M−1 s−1, respectively. The dependence of the transient absorption on the pH shows that the OH adduct has a pKa value of 4.7.
  • Ken-ichi Machida, Michio Enyo
    1986 Volume 59 Issue 3 Pages 725-731
    Published: 1986
    Released: June 27, 2006
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    Hydrogen electrode reactions (HER) on thin-layer electrodes of group-IB and VIII metals (Cu, Ag, Au, Ni, and Pt) prepared by electro-deposition on Pd foil substrates were studied (together with the Pd foil itself) in 0.5 M H2SO4 and 1.0 M NaOH (M=mol dm−3) at 303 K by a transient technique. The reactions on these metals were concluded to proceed via a Volmer-Tafel reaction route and the exchange current densities of the elementary steps, ioV and ioT, were then evaluated. The electrocatalytic activities towards the Volmer step were observed to be in the order Pt>Pd>Au>Ag>Cu in an acidic solution and Pt>Pd>Ni≥Ag≥Au≥Cu in an alkaline solution. The activities towards the Tafel step were Pt≥Pd>Au>Cu>Ag in an acidic solution and Pd>Pt>Au>Cu=Ag>Ni in an alkaline solution. The results were summarized in terms of the parameter mo (=ioVioT). This parameter was used to describe the electrochemistry of the energy efficiency of a hydride-type hydrogen-storage electrode, when the metals were employed for the purpose of modifying the electrode surface. Pt and Ag (among the group-IB metals) in both acidic and alkaline solutions were revealed to be suitable electrocatalysts.
  • Yasuyuki Takeda, Akio Tanaka
    1986 Volume 59 Issue 3 Pages 733-735
    Published: 1986
    Released: June 27, 2006
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    Enthalpy (ΔHex) and entropy changes (ΔSex) for overall extractions of alkali metal (Na, K, Rb, and Cs) picrates with 18-crown-6 (18C6), and those (ΔHD,L and ΔSD,L) for distribution of 18C6 itself were determined between CHCl3 and water, all the extracted complexes being 1:1:1 complexes. The ΔHex and ΔSex values of 18C6 for all the alkali metals are negative. The ΔHD,L and ΔSD,L values of 18C6 are both positive. Enthalpy (ΔHex′) and entropy changes (ΔSex′) for ion-pair extractions of 18C6-alkali metal ion complexes with picrate anions were calculated. All the ΔHex′ and ΔSex′ values are negative except for ΔSex′ value of Na (positive). The ion-pair extractions were discussed from the thermodynamic point of view.
  • Junko Motonaka, Hiroshi Konishi, Sanae Ikeda, Nobuyuki Tanaka
    1986 Volume 59 Issue 3 Pages 737-740
    Published: 1986
    Released: June 27, 2006
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    In an investigation on the behavior of a cadmium ion-selective electrode in methanol–water and ethanol–water mixtures, potential measurements were carried out with a digital pH/mV meter, a cadmium ion-selective indicator electrode and a silver–silver chloride reference electrode. The calibration curves, slopes of the response, response times, effects of temperature, relation between the potential and the pH-meter reading and selectivity of the electrode were discussed. The response of cadmium ions (electromotive force) was linear between 10−7–10−2 mol dm−3 in water. However, the linear range became narrower with an increase in the alcohol content. The slopes in alcohol–water mixtures (27–33 mV/decade in methanol–water mixtures, 21–29 mV/decade in ethanol–water mixtures) were nearly equal to the Nernstian slope (29.6 mV/decade). The response times of the cadmium ion-selective electrode in 99 v/v% methanol and in 99 v/v% ethanol were somewhat long, but were still within 5 min for all solutions consisting of 10−5–10−1 mol dm−3 of cadmium ions. The selectivity of the cadmium ion-selective electrode in various media was examined by the mixed-solution method using potassium, sodium, calcium and magnesium ions as the interfering ions. It was found that a cadmium ion-selective electrode could be used to determine cadmium ions in an alcohol–water solution, although the response time became longer and the linear range of the response became narrower with an increase in the alcohol content.
  • Yasuyuki Miura, Tomozo Koh
    1986 Volume 59 Issue 3 Pages 741-745
    Published: 1986
    Released: June 27, 2006
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    A method has been developed for the determination of micro amounts of thiocyanate. It is based on the reaction of thiocyanate with a given amount of permanganate as an oxidizing agent in a dilute sulfuric acid medium and on the spectrophotometric measurement of iodine as triiodide, which is formed by the oxidation of iodide with an excess of permanganate for its reaction with thiocyanate. The conditions for the thiocyanate to be quantitatively oxidized were established by varying the temperature, reaction time, and amounts of sulfuric acid and permanganate. The present method can be successfully applied to the determination of thiocyanate in the range from 7×10−7 to 4×10−5 mol dm−3 (0.4–23.2 μg SCN in 10 cm3). In eleven determinations for 10-cm3 sample solutions containing 0.250 μmol of thiocyanate, the present method gave a mean value of 0.251 μmol, with a standard deviation of 0.0022 μmol and a relative standard deviation of 0.88%. Chloride, bromide, iodide, and cyanide did not interfere with the determination of 14.5 μg of thiocyanate in the presence of 1000 μg, 500 μg, 100 μg and 50 μg, respectively.
  • Shoji Kajigaeshi, Takashi Nakagawa, Noritaka Nagasaki, Hiromichi Yamas ...
    1986 Volume 59 Issue 3 Pages 747-750
    Published: 1986
    Released: June 27, 2006
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    Reaction of primary alcohols or simple ethers, α,ω-diols or cyclic ethers, and secondary alcohols with sodium bromate in the presence of catalytic amount of hydrobromic acid under mild conditions gave dimeric esters, lactones, and ketones in fairly good yields, respectively.
  • Wakichi Fukuda, Hozumi Sato, Hiroshi Kakiuchi
    1986 Volume 59 Issue 3 Pages 751-756
    Published: 1986
    Released: June 27, 2006
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    Reactions of chloromercurio aldehydes with acyl chlorides gave a variety of (Z)- and (E)-enol esters. The Z/E ratio of the enol esters is dependent on the structure of chloromercurio aldehydes but independent of that of acyl chlorides. Z-Rich enol esters were prepared by acylation of 2-chloromercurio aldehydes derived from propanal, butanal, and 2-phenylethanal, while E-rich 1-acyloxy-1,3-butadiene was obtained by acylation of (E)-4-chloromercurio-2-butenal. Reaction mechanisms for the stereoselective formation of these enol esters are discussed together with the isomer composition of starting enol acetates from which the chloromercurio aldehydes were prepared.
  • Toshio Koizumi, Toshio Fuchigami, Zaghloul El-Shahat Kandeel, Norio Sa ...
    1986 Volume 59 Issue 3 Pages 757-762
    Published: 1986
    Released: June 27, 2006
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    It was confirmed that the cathodic crossed coupling of acetone with unsaturated compounds in aqueous sulfuric acid could proceed smoothly, when the compounds which had radical-acceptable double bonds and were adsorbed on a mercury cathode were used. From this fact, it was concluded that the coupling occurs via the addition of a radical intermediate formed by the one-electron reduction of acetone to the double bonds on the cathode surface. Possibility of the addition of an anionic intermediate derived from acetone was excluded by no occurrence of the coupling of acetone with a polar acetylenic triple bond compound adsorbed on the cathode.
  • Hiroatsu Matsuura, Koichi Fukuhara
    1986 Volume 59 Issue 3 Pages 763-768
    Published: 1986
    Released: June 27, 2006
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    Hydration of the oxyethylene chain was studied by a Brillouin-scattering method; hypersonic velocities in aqueous solutions of CH3(OCH2CH2)mOCH3 with m=1–4 and CH3(OCH2CH2)mOH with m=2 and 3 were measured. The concentration of the solution, at which the sound velocity gave a maximum value, led to the number of water molecules, at the highest hydration, per ether linkage in the oxyethylene chain. The experimental results showed that 1.8 water molecules take part in the hydration of each –CH2OCH2– group and that the number of the water molecules is virtually constant independently of the oxyethylene-chain length as far as the number of the oxyethylene units is limited up to four. These findings indicate that a sort of hydration complex of approximately 1 –OCH2CH2–:2 H2O is formed in the aqueous solution. It is suggested that the stabilization of the gauche conformation for the OCH2–CH2O group in aqueous solution, as evidenced by Raman-spectroscopic observations, is promoted greatly by the hydrogen bond of water molecules which are bridged between the adjacent ether oxygens in the oxyethylene chain.
  • Hiroshi Maeda, Yoriko Tanaka, Shoichi Ikeda
    1986 Volume 59 Issue 3 Pages 769-773
    Published: 1986
    Released: June 27, 2006
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    The induction of the β-structure of fully ionized poly[S-(2-carboxyethyl)-L-cysteine] in solution markedly depended on the kind of head group of cationic surfactants; it occurred by the addition of dodecylammonium chloride (DAC) but not by the addition of dodecyldimethylammonium chloride (DDAC) or dodecyltrimethylammonium chloride (DTAC), as concluded based on circular dichroism spectra. The induction of the β-structure by DAC was not inhibited by raising ionic strength of the medium but was enhanced when the polypeptide concentration was increased. The polypeptide took the β-structure in the precipitates produced by the addition of any one of these three surfactants, as indicated by the infrared absorption (IR) spectra. Intensity of a characteristic absorption band of carboxylate group around 1570 cm−1 for the complex with DDAC was vanishingly weak, while those with DAC and DTAC were medium and strong, respectively. The precipitates were solubilized in the presence of excess amount of surfactants. In the solubilized solution, the β-structure was again found in the case of DAC, irrespective of the polypeptide concentration, but it was found only at high polypeptide concentrations in the case of DDAC.
  • Masashi Tanaka
    1986 Volume 59 Issue 3 Pages 775-779
    Published: 1986
    Released: June 27, 2006
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    Optical reflection and magnetic susceptibility measurements of (DBTTF)2(Cu2Cl6) and (DBTTF)2(Cu2Br6) complexes were carried out. The analysis of the reflection spectra of the single crystals of these complexes shows that the electronic structure of DBTTF+ cation molecules is typical of the dimer type configuration. The magnetic susceptibilities of these complexes were measured over a temperature range of 2–300 K. The magnetic behavior conforms to a modified Bleaney-Bowers equation, indicating the existence of the spin coupling within the Cu2Cl62− or Cu2Br62− dimers and the antiferromagnetic spin interaction between Cu2Br62− dimers.
  • Tadaaki Kakutani, Yoshinori Nishiwaki, Toshiyuki Osakai, Mitsugi Senda
    1986 Volume 59 Issue 3 Pages 781-788
    Published: 1986
    Released: June 27, 2006
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    The question of the site of ionophore–ion complex formation, whether it is in the organic phase (EC), in the aqueous phase (CE), or at the interface (E), in the transfer facilitated by dibenzo-18-crown-6 of sodium ion across the nitrobenzene/water interface was studied by kinetic analysis of the ion transfer using a.c. polarographic method. The results indicate that the interface reaction mechanism (E) is the most probable of the three.
  • Hiromichi Yamada, Hisao Hayashi, Yukio Fujii, Masateru Mizuta
    1986 Volume 59 Issue 3 Pages 789-794
    Published: 1986
    Released: June 27, 2006
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    Extraction of aluminum(III) and indium(III) with decanoic acid in 1-octanol was carried out at 25 °C and at an aqueous ionic strength of 0.1 mol dm−3 (NaClO4). Monomeric and tetrameric aluminum(III) decanoates and monomeric indium(III) decanoate are responsible for the extraction. From a comparison of the present results with those obtained from the previous works, the polymerization of the extracted species was found to be more extensive in benzene than in 1-octanol, and the metal decanoates were highly polymerized in the following order in both solvents: Al>Ga>In.
  • Yoshihiro Kudo, Noboru Yoshida, Masatoshi Fujimoto
    1986 Volume 59 Issue 3 Pages 795-802
    Published: 1986
    Released: June 27, 2006
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    The formation of N,N-bidentate 1:2 complexes of nickel(II) with various N,N,O-terdentate 2-(2-pyridylazo)phenolic ligands was detected spectrophotometrically in ethyl acetate and was examined with respect to the influences of Brønsted bases, the counter anions in the nickel(II) salts employed, solvent basicity, and the steric requirements around the donor nitrogen atoms in the ligand in the 1:2 complex. It is concluded that the stability of the N,N-bidentate complex species in solutions predominantly depends on the basicity of the counter anions X in NiX2 and of the solvent. In the case of 1-(2-pyridylazo)-2-naphthol, owing to a high steric hindrance of the naphthalene ring, the formation of the N,N-bidentate complex was not observed even in the solvent of low basicity such as dioxane.
  • Kazuo Haga, Katsumasa Iwaya, Ryohei Kaneko
    1986 Volume 59 Issue 3 Pages 803-807
    Published: 1986
    Released: June 27, 2006
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    The condensations of 1,4-cyclohexanedione with several diphenylamines were investigated in order to determine the limit of the utility of this reaction for the N-phenylation of aromatic secondary amines. 4-Methoxy-, 4,4′-dimethyl-, and 4,4′-dibromodiphenylamines produced their N-phenylated compounds in fairly good yields, but 4-hydroxy-, 3-methoxy-, and 4,4′-bis(dimethylamino)diphenylamines produced poor yields. Nitro-substituted diphenylamines gave N-phenyl derivatives in low yields along with N-4-hydroxyphenyl derivatives. N,N′-Diphenyl-p-phenylenediamine and N,N′-diphenylbenzidine gave corresponding tetra-N-phenyl diamines in good yields. The condensation of N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, di-2-pyridylamine, phenothiazine, and carbazole with 1,4-cyclohexanedione were also examined.
  • Makoto Nakazawa, Yasushi Mizobe, Yoichi Matsumoto, Yasuzo Uchida, Megu ...
    1986 Volume 59 Issue 3 Pages 809-814
    Published: 1986
    Released: June 27, 2006
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    The potential-current relationships of DMF solutions of a series of iron–sulfur compounds have revealed that in the presence of clusters [Fe4S4(SR)4]2− (R=PhCH2 or But) and [M2Fe6S8(SEt)9]3− (M=Mo or W) the electroreduction of CO2 proceeds at the potential shifted by about 0.7 and 0.5 V, respectively, to the positive direction compared to the potential at which CO2 is reduced without any catalyst. When controlled potential electrolysis of a DMF solution containing [Fe4S4(SCH2Ph)4]2− was carried out under CO2 at −2.0 V vs. SCE, phenylacetate and formate were formed as the products resulting from CO2 reduction. The cubane structure of this cluster collapsed rapidly under these conditions. However, when excess amount of PhCH2SH was added to the catholyte, the cluster structure was preserved during a relatively long period of electrolysis, and the yield of phenylacetate increased but that of formate decreased compared with the reaction in the absence of free PhCH2SH.
  • Kunio Ito, Shingo Miyajima
    1986 Volume 59 Issue 3 Pages 815-818
    Published: 1986
    Released: June 27, 2006
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    (Z)-4,4-Dimethyl-5-oxo-2-pentenoic acid (1) exists almost exclusively in the hydroxy lactone form, the tautomeric equilibrium constant (K=[Ring]/[Chain]) being 2.8×103 in water as estimated by the pKa method. Several examples are described of preference for ring forms of derivatives of 1, which are capable of exhibiting ring-chain tautomerism. (E)-4,4-Dimethyl-5-oxo-2-pentenoic acid (7) reacts with thionyl chloride to afford a trimeric chloro lactone, which on treatment with water or aniline gives the corresponding hydroxy or anilino lactone. Compound 1 or 7 reacts with a variety of phenylhydrazines to yield dihydropyrazole derivatives, except for 2,4-dinitrophenylhydrazine which on reaction with 1 gives a 2,4-dinitrophenylhydrazino lactone.
  • Tetsuo Suami, Seiichiro Ogawa, Makoto Takata, Kuninobu Yasuda, Kiyoshi ...
    1986 Volume 59 Issue 3 Pages 819-821
    Published: 1986
    Released: June 27, 2006
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    Pseudo-β-DL-fructopyranose was synthesized from DL-1,2-di-O-acetyl-(1,3/2)-3-bromomethyl-5-cyclohexene-1,2-diol by a six steps reaction: Dehydrobromination, epoxidation, acetolysis, reduction, and deacetylation, in overall yield of 4.8%. Pseudo-β-DL-fructopyranose was found to be nearly as sweet as D-fructose which is the most sweet sugar known in naturally occurring carbohydrates.
  • Keisuke Mita
    1986 Volume 59 Issue 3 Pages 823-826
    Published: 1986
    Released: June 27, 2006
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    Kinetic studies on the catalytic hydrogenation of benzil to benzoin by bis(dimethylglyoximato)cobalt(II), Co(Hdmg)2, were carried out by varying the concentration of Co(Hdmg)2 and pyridine. The initial rate of the hydrogenation reaction was first order with respect to the overall cobalt concentration at a constant overall pyridine concentration. On the other hand, the rate passed through a peak as the overall pyridine concentration was increased at a constant overall cobalt concentration. The peak was observed at [py]T=130 mmol dm−3, where the square bracket denotes the concentration in the liquid phase. These results show that the initial reaction rate, Vin, can be expressed by the following rate equation,
    Vin=k[Co(Hdmg)2]\frac58[py]T1+58[py]T,
    where, k=1.1 min−1.
  • Sadakatsu Nishikawa, Ryutaro Shinohara, Goro Tanaka
    1986 Volume 59 Issue 3 Pages 827-832
    Published: 1986
    Released: June 27, 2006
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    Ultrasonic absorption in the frequency range of 6.5 to 220 MHz has been measured in aqueous solutions of 3-methoxy-3-methyl-1-butanol and 2-t-butoxyethanol as a function of the concentration along with the measurement of sound velocity at 1.92 and 2.5 MHz at 25°C. A single relaxational ultrasonic absorption has been found in both solutions and it is interpreted by a reaction kinetics associated with the interaction between solute and solvent, AB \ ightleftharpoons A+B where AB is the complex, A the solute and B the solvent. The forward and backward rate constants for the interaction have been determined from the concentration dependence of the relaxation frequencies to be kf=1.4×108 s−1 and kb=1.1×108 mol−1 dm3 s−1 for 3-methoxy-3-methyl-1-butanol solution and kf=9.0×107 s−1 and kb=1.3×108 mol−1 dm3 s−1 for 2-t-butoxyethanol solution. The water structure has also been estimated from the absorption data and it has been clarified for the water structure promoted by additions of such solutes. Correlations between the structures of the solutes and the ultrasonic properties of the solutions are discussed in terms of the hydrophobicity of the solutes.
  • Haruo Nakayama, Hideyuki Usui
    1986 Volume 59 Issue 3 Pages 833-837
    Published: 1986
    Released: June 27, 2006
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    The solid–liquid phase diagrams of binary mixtures of water with tetrabutylammonium alkanesulfonate (n-C4H9)4NO3SR(R=CH3–C5H11) and with tetrabutylammonium benzenesulfonate were examined in order to confirm the formation of clathrate-like hydrates. It has been found that (1) all the sulfonates examined can form clathrate-like hydrates with hydration numbers either around 30 or around 39; (2) these hydrates can be classified into three groups I, II, and III on the basis of the hydration numbers and melting points just as in the case of a series of tetrabutylammonium carboxylate hydrates; and (3) generally, the melting points of these sulfonate hydrates are lower than those of tetrabutylammonium carboxylate hydrates. The formation of clathrate-like hydrates of tetrabutylammonium hydrogensulfite and of tetrabutylammonium sulfite has also been reported and is discussed in an appendix.
  • Ikuo Tokue, Yoshio Ito
    1986 Volume 59 Issue 3 Pages 839-842
    Published: 1986
    Released: June 27, 2006
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    Emission spectra of the fragments of Isothiocyanic acid (HNCS) produced by electron impact were studied. The onset for formation of NH(A3Π) is 9.2±0.5 eV. On the basis of the excitation function of the NH(A–X) band, NH(A) is shown to be formed via a spinforbidden process HNCS→NH(A3Π)+CS(X3Σ+) near the onset. At higher energies, a spin-allowed process HNCS→NH(A)+CS(a3Π) seems to be predominant. The ratio of the formation rate of NH(c) to that of NH(A) is 0.18±0.03.
  • Norimichi Sano, Jiro Tanaka
    1986 Volume 59 Issue 3 Pages 843-851
    Published: 1986
    Released: June 27, 2006
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    Reflection spectra were measured on two polymorphs of (5-dimethylamino-2,4-pentadienylidene)dimethylammonium perchlorate in order to determine the origin of the J band. One polymorph exhibited two bands with different polarization characteristics; one of them is explained by the molecular-exciton (MX) band of a ππ* transition character and the other is an intermolecular charge-resonance (CR) band, the polarization being along the direction connecting the nitrogen atoms of the adjacent molecules. The other polymorph exhibited a quasi-metallic reflection due to the overlapping of the CR and MX bands.
  • Takao Iijima
    1986 Volume 59 Issue 3 Pages 853-858
    Published: 1986
    Released: June 27, 2006
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    The method of vibrational corrections for a molecule which has a large amplitude intramolecular motion has been revised and applied to the determination of the zero-point average structure of methylamine. Necessity of torsional correction for this type of molecules has been pointed out and the method has been presented. A recent result of electron diffraction was jointly used with the effective moments of inertia obtained by microwave spectroscopy by Takagi and Kojima. The structural parameters in rz and \varphiz with the estimated limits of error in parentheses are: r(C–N)=1.471(3) Å, r(C–H)=1.101(3) Å, r(N–H)=1.019(6) Å, ∠HCH=108.4(5)°, ∠HNH=106.0(6)°, and ∠CNH=111.5(7)°. Deuterium isotope effects in the structural parameters were also determined.
  • Kazuo Kojima, Jiro Matsuda
    1986 Volume 59 Issue 3 Pages 859-863
    Published: 1986
    Released: June 27, 2006
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    The optical absorption spectra of single crystals of [N(CH3)4]2[CoCl4] and [N(CH3)4]2[CoBr4] have been measured over the range of 4000–33000 cm−1 at the temperature of liquid nitrogen and at room temperature. The spectra have been analyzed using the crystal-field theory which includes spin-orbit coupling. Some discussion of the Racah parameter B and of the 4T1(4F) and 4T1(4P) states is presented.
  • Toshishige M. Suzuki, Toshiro Yokoyama, Hideyuki Matsunaga, Tetsuo Kim ...
    1986 Volume 59 Issue 3 Pages 865-868
    Published: 1986
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Macroreticular styrene-divinylbenzene copolymers functionalized with iminodiacetic acid and diethylenetriamine-N,N,N″,N″-tetraacetic acid have been examined in order to apply them to the selective recovery of gallium(III) and/or indium(III) from acidic solutions. The equilibrium adsorption capacities, distribution coefficients, and metal-adsorption rates of the polymer resins for Group IIIb ions and other common metal ions have been studied. The selectivity sequence of the present resins are as follows: Fe(III)>In(III)>Ga(III)\simeqCu(II)>Zn(II)>Al(III). The selective recovery of In(III) and/or Ga(III) from acidic solutions has been demonstrated using a column of the present resins.
  • Junji Kimura, Hideyuki Kobayashi, Osamu Miyahara, Oyo Mitsunobu
    1986 Volume 59 Issue 3 Pages 869-874
    Published: 1986
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    2,6-Di-t-butyl-4-nitrophenol reacted with O2-methyluridine, N3-methyluridine or 4-triazolyl-1-(β-D-ribofuranosyl)-2(1H)-pyrimidinone in the presence of diethyl azodicarboxylate and triphenylphosphine selectively at the 5′-position to give the corresponding 4-(nucleosid-5′-yl-aci-nitro)-2,6-di-t-butylcyclohexa-2,5-dienone (aci-nitro ester of nucleoside) in 39–72% yields along with varied amounts of 5′-deoxy-5′-[N,N′-bis(ethoxycarbonyl)hydrazino]nucleosides. By comparison of the reactions of pyrimidine nucleosides having free 2′- and 3′-hydroxyl groups with those of their 2′,3′-O-isopropylidene derivatives, the ratio of aci-nitxo ester to 5′-deoxy-5′-hydrazinonucleoside was affected by the protecting groups as well as the time required for the addition of diethyl azodicarboxylate to a solution of other reactants. Similarly, N1,N6,2′3′-O-tetrabenzoyladenosine afforded the expected aci-nitro ester in 83% yield. The aci-nitro esters prepared were successfully reacted with stabilized phosphoranes such as (ethoxycarbonylmethylene)triphenylphosphorane or (acetylmethylene)triphenylphosphorane giving 1-[(E)-β-D-ribo-hept-5-enofuranosyl]- or 1-[(E)-β-D-ribo-oct-5-enofuranosyl]-pyrimidines and -purines. When the two stage reactions were carried out by one-pot procedure without isolation of aci-nitro esters, overall yields of alkenofuranosylpyrimidines were markedly improved.
  • Shigeru Nishiyama, Yoichi Ikeda, Shosuke Yamamura
    1986 Volume 59 Issue 3 Pages 875-878
    Published: 1986
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    In connection with the daphniphyllum alkaloids, some 6-oxa- and 2,8-dioxabicyclo[3.2.1]octanes, which are included as a partial structure of daphmacrine and codaphniphylline, have been synthesized starting from geraniol.
  • Nan Xing Hu, Yoshio Aso, Tetsuo Otsubo, Fumio Ogura
    1986 Volume 59 Issue 3 Pages 879-884
    Published: 1986
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Polystyrene-bound diaryl selenoxide and telluroxide have been prepared, which behaved as mild oxidizing agents for thiols to disulfides, phosphines to phosphine oxides, hydroquinone and catechol to p- and o-benzoquinones, and thioketones to oxo compounds. The telluroxide completed these reactions in shorter periods or under milder conditions than the selenoxide. In addition, they effected novel solvent-dependent reactions of thioamides involving thioureas to 1,2,4-thiadiazoles or to nitriles. In nonacidic solvents, the dehydrosulfurization to nitriles occurred in preference to the oxidative dimerization to 1,2,4-thiadiazoles, but an acidic solvent such as acetic acid promoted the latter reaction.
  • Yoshio Inoue, Masanori Toyofuku, Masaaki Taguchi, Shin-ichi Okada, Har ...
    1986 Volume 59 Issue 3 Pages 885-891
    Published: 1986
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Direct α-allylation of a variety of ketones and aldehydes with 2-allylisourea took place in the presence of a catalytic amount of a palladium(0) complex under neutral and mild conditions. Scope and limitations of this novel method have been investigated.
  • Yoshiyuki Kobayashi, Shoichi Asada, Ichigen Watanabe, Hiroaki Hayashi, ...
    1986 Volume 59 Issue 3 Pages 893-895
    Published: 1986
    Released: June 27, 2006
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    Using cyclo((S)-phenylalanyl-(S)-histidyl) as catalyst, optically active cyanohydrins from substituted benzaldehydes with p-methyl, m-methyl, o-methyl, m-methoxyl, or m-phenoxyl group were obtained with optical yield of 82–33%. For the asymmetric cyanohydrin synthesis, nonpolar solvent such as benzene or carbon tetrachloride was advantageous, while no asymmetric synthesis took place in methanol or dimethyl sulfoxide.
  • Yoshiaki Kurauchi, Hideo Nobuhara, Kazuya Ohga
    1986 Volume 59 Issue 3 Pages 897-905
    Published: 1986
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The irradiation of aqueous solutions of 1-methyl-2-phenyl-1-pyrrolinium perchlorate (1) in the presence of α-hydroxyalkanoate anions led to the formation of 2-(hydroxyalkyl)pyrrolidine adducts and a reduction product, 1-methyl-2-phenylpyrrolidine. Mechanistic studies demonstrated that photoaddition reactions were induced by one-electron transfers from the carboxylato groups of alkanoates to the excited singlet state of 1 (1S1), followed by an efficient decarboxylation. Furthermore, the photoreaction of 1 with ethoxyacetate was found to give a 2-(ethoxymethyl)pyrrolidine adduct in preference to the reduction product. For photoreactions with 2-mercaptopropionate and α-amino acids, the reduction product was detected. N-Acetylglycinate gave a 2-(acetylaminomethyl)pyrrolidine adduct in fairly high yield (80%). The features of these photoreactions with α-heteroatom-substituted alkanoates are discussed in terms of fluorescence-quenching efficiencies and the properties of radicals formed through electron transfers to 1S1.
  • Iwao Watanabe, Keiichi Maya, Yoshiki Yabuhara, Shigero Ikeda
    1986 Volume 59 Issue 3 Pages 907-913
    Published: 1986
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The threshold energies Et of photoelectron emission by solutions (PEES) were determined for several butylamines in acetonitrile and water. The correlations between Et and gas-phase ionization potential Ip and oxidation potential Eox were found to be linear. The difference between Et and Ip originates from the electronic polarization energy of solvent molecules and the polarization energy was found to be inversely proportional to the solvation radius in accordance with the Born solvation free energy model. The Et values were also compared with Eox to discuss the reorientation relaxation of solvent molecules in the electron transfer process. The selective coverage of aqueous solution surface with amine molecule was indicated by the PEES technique.
  • Hiroyuki Ishida, Ryuichi Ikeda, Daiyu Nakamura
    1986 Volume 59 Issue 3 Pages 915-924
    Published: 1986
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Four solid phases of CH3NH3I named as α′, β′, δ, and ε were studied by the temperature dependence of 1H spin-lattice relaxation time T1 and 1H spin–spin relaxation time T2 (for ε) at several NMR frequencies, and of 1H NMR second moment. Phase transitions were studied by means of differential thermal analysis and 1H T1. The X-ray powder patterns of the highest-temperature ε phase taken at ca. 440 K revealed that the crystal forms a CsCl-type cubic lattice. The measurements of differential scanning calorimetry gave unusually small entropy of melting indicating that the cations of the ε phase are in a state having the most part of their motional freedom. From 1H NMR T1 experiments, it was found that the transformation of the room-temperature α′ phase to the low-temperature stable β′ phase needed longer time than three months at Dry Ice temperature for samples carefully purified and dried for a long time under vacuum whereas it was completed within two weeks for roughly dried samples. The NMR results indicated that the cations are bound tightly in the β′ phase whereas they are fairly free to reorient in the low-temperature substable δ phase. In the α′ phase, the cations perform C3 reorientations very rapidly about their C–N bond axis. The cations of the ε phase undergo overall rotation as well as self-diffusion which was confirmed by electrical conductivity measurements. The mechanism of the self-diffusion of the cations is discussed.
  • Ken-ichi Machida, Michio Enyo, Gin-ya Adachi, Hiroki Sakaguchi, Jiro S ...
    1986 Volume 59 Issue 3 Pages 925-926
    Published: 1986
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Hydrogen storage type electrodes were fabricated from LaNi5 powder after coating with group-IB metals by an electroless plating method, followed by press moulding. The hydrogen electrode reaction (HER) characteristics and mechanical stability during hydrogen charge/discharge cycles were then studied in 1.0 M (M= mol dm−3) NaOH.
  • Akira Kasahara, Taeko Izumi, Satoshi Murakami, Hiroshi Yanai, Masayuki ...
    1986 Volume 59 Issue 3 Pages 927-928
    Published: 1986
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    In the presence of palladium(II) chloride, 2-bromoanilines readily react with the methyl vinyl ketone and the ethyl acrylate to produce vinylogous arylamino ketones and esters. A palladium(0)-assisted cyclization of the arylamino ketones and the esters leads to a formation of 3-substituted indoles.
  • Toshikazu Ibata, Makoto Kashiuchi
    1986 Volume 59 Issue 3 Pages 929-930
    Published: 1986
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The Cu(acac)2-catalyzed decomposition of α-diazoacetophenones in the presence of bis(p-methoxyphenyl) selenide (3) did not give the corresponding selenonium ylide but gave r-1,c-2,t-3-tribenzoylcyclopropanes through the successive reaction of the intermediary selenonium ylide. On the other hand, the reaction of diazodimedone with 3 gave bis(p-methoxyphenyl)selenonium 4,4-dimethyl-2,6-dioxocyclohexylide.
  • Kazuhiko Saigo, Naomi Kubota, Shoko Takebayashi, Masaki Hasegawa
    1986 Volume 59 Issue 3 Pages 931-932
    Published: 1986
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    (±)-1,2-Diphenylethylenediamine (DPEDA) was efficiently resolved by the fractional crystallization of its diastereomeric salts with optically active mandelic acid. 1H-NMR spectrum of N-monoacylated DPEDA with an optically active derivatizing agent showed that DPEDA thus obtained was optically pure.
  • Koichi Kobayashi, Kyo Takaoka
    1986 Volume 59 Issue 3 Pages 933-934
    Published: 1986
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Electron spectroscopy for chemical analysis (ESCA) was used to determine the composition of icosanoic acid (n-C19H39COOH) monolayer deposited on the microscope glass slide from the water surface containing Cd2+ at varying pH. It was found that the monolayers deposited from substrate at pH<4.6, pH>6.6, and pH=4.6–6.6 consist of icosanoic acid, cadmium icosanoate, and mixture of both substances, respectively.
  • Masayuki Nakagaki, Shoko Yokoyama
    1986 Volume 59 Issue 3 Pages 935-936
    Published: 1986
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The order of effectiveness of 1-alkanols for increasing the rate of acid-catalyzed hydrolysis of sodium dodecyl sulfate is 1-dodecanol>1-tetradecanol >> 1-decanol. The effect of 1-alkanols on this hydrolysis is discussed from the viewpoint of formation of complexes composed of SDS and 1-alkanol.
  • Hirofumi Kawazumi, Tuneaki Uchida, Teiichiro Ogawa
    1986 Volume 59 Issue 3 Pages 937-938
    Published: 1986
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The laser-induced fluorescence of molecular ions, N2+ (X, 2Σg+), was measured under the controlled electron-impact ionization of N2 in the thermal gas jet. The effective rotational temperature of N2+ (X) increased from 320±5 K to 367±15 K for the incident electron energy from 750 eV to 17 eV.
  • Masataka Moriyasu, Atsushi Kato, Yohei Hashimoto
    1986 Volume 59 Issue 3 Pages 939-940
    Published: 1986
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Rotamers of N-alkyl-substituted amides have been separated by means of high-performance liquid chromatography(HPLC) at low column temperatures. The ratios of the E-rotamers have been found to increase in the following order: propionamides<acetamides<formamides.
  • Joichi Ueda, Yukiko Fukazawa, Yuu Koizumi
    1986 Volume 59 Issue 3 Pages 941-942
    Published: 1986
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Sarcosinexylenol Blue (SXB) was synthesized and the possibility of using SXB as a spectrophotometric reagent was examined. The fundamental conditions for the photometric determination of nickel which gave relatively strong coloration with SXB were studied. The simultaneous determination of nickel and zinc was also studied.
  • Akira Imamura, Toshiya Okajima, Katsuya Kanda
    1986 Volume 59 Issue 3 Pages 943-945
    Published: 1986
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Molecular orbital calculations were performed for the study of the mechanism of the mutarotation of D-glucose (in Fig. 1) by the CNDO/2 method. The calculated results for a proposed mechanism are in good agreement with the experimental results in relation to the effect of the acid and the base, suggesting the validity of the proposed mechanism of mutarotation.
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