Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 51 , Issue 8
Showing 1-50 articles out of 62 articles from the selected issue
  • Masao Matsui, Masashi Imamura
    1978 Volume 51 Issue 8 Pages 2191-2194
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    Binary mixtures of tetrahydrofuran (THF) with benzene, thiophene, and nitrobenzene were subjected to radiolysis with γ-rays. The THF–benzene mixture was also irradiated with 28.6 MeV 4He- and 90.9 MeV 12C-ions. For THF–benzene mixtures, similar deviations of G(H2) from the mixture law were observed for all the radiolyses; these results are regarded as being due to energy transfer from THF+, the precursor of hydrogen, to benzene. The total ionization yield of THF was calculated as 3.0–3.3 in G-units, irrespective of radiation and additives. This is on the basis of Hardwick’s procedure, in which the deviations of G(H2) are divided by the efficiency of the energy transfer. This result also indicates that the total ionization yield is independent of the nature of radiation, whose LET range is from 0.02 to 49.2 eV/Å.
  • Masamichi Akimoto, Masahiro Usami, Etsuro Echigoya
    1978 Volume 51 Issue 8 Pages 2195-2199
    Published: 1978
    Released: April 19, 2006
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    The reactivity of V4+ with gaseous oxygen formed on various kinds of supported V2O5 catalysts has been investigated by ESR. The results are discussed as carrier effect in relation to the selectivity for maleic anhydride formation during the course of the vapor-phase oxidation of butadiene. V4+ formed on Al2O3 (V/Al≤10/90 atom ratio) and MgO (V/Mg≤30/70) showed a hyperfine ESR structure and was hardly oxidized whereas V4+ formed on SiO2 (V/Si≥5/95) had the singlet ESR signal and was easily oxidized. Formation of these two kinds of V4+ was observed on V2O5–Al2O3 (V/Al≥20/80). They were similarly observed in the case of V2O5-TiO2, but some portion of V4+ having the hyperfine structure was also oxidized. The selectivity was high over the catalysts forming the reactive V4+ as compared with those forming the unreactive one. The reactive V4+ was shown by X-ray diffraction to be preferentially formed in crystalline V2O5. Study of the reduction and reoxidation of unsupported crystalline V2O5 by means of IR and the effect of addition of alkali metal oxide on the catalytic activity of the supported V2O5 were discussed. The important role of double bond type lattice oxygen V=O in maleic anhydride formation was proposed.
  • Hitoshi Kanazawa, Tohru Kawai, Yuji Ohashi, Yoshio Sasada
    1978 Volume 51 Issue 8 Pages 2200-2204
    Published: 1978
    Released: April 19, 2006
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    The structure of N-carboxy-γ-benzyl-L-glutamate anhydride has been determined by X-ray analysis. The crystal is orthorhombic; space group, P212121; Z=4 with a=7.766(1), b=27.470(4), and c=5.948(1) Å. The structure was deduced by the direct method and refined to a final R value of 0.057 for 1504 observed reflections by the block-diagonal least-squares method. The hydrogen bond is formed between the imino group and the carbonyl group of the side chain. The dimension of the five-membered ring is affected by the intermolecular hydrogen bond as compared with the crystal structures of the other N-carboxy anhydrides of α-amino acid.
  • Hitoshi Kanazawa, Tohru Kawai, Yuji Ohashi, Yoshio Sasada
    1978 Volume 51 Issue 8 Pages 2205-2208
    Published: 1978
    Released: April 19, 2006
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    The crystal structure of N-carboxy-L-leucine anhydride has been determined by means of X-ray. The crystal is orthorhombic; space group, P212121; Z=4 with a=6.527(1), b=23.920(4), and c=5.527(1) Å. The structure was deduced by the direct method and refined to the final R value 0.049 for 624 observed reflections by the block-diagonal least-squares method. The N-carboxy anhydride rings are arranged in a layer form sandwiched by hydrophobic side chains. The highest polymerizability of this compound in the crystalline state is due to the sandwich structure.
  • Kazuyoshi Tanaka, Kenichi Fukui
    1978 Volume 51 Issue 8 Pages 2209-2214
    Published: 1978
    Released: April 19, 2006
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    A concept of the cross-bicyclization complementary to that of the cycloaddition is defined for interpreting the mechanism of the simultaneous bicyclizations in linear conjugated polyenes based on the perturbation treatment in the frame of Hückel MO’s. Stereoselective modes in thermal and photo-induced reactions are shown to depend on the sign of the bond-bond-polarizability, Πrs,tu, of the concerned polyene, where r, s, t, and u refer to the atomic positions at which the bicyclization occurs. From the properties of Πrs,tu of linear conjugated polyenes, these modes are simply determined by the relationship among r, s, t, and u in thermal cases, but not in photo-induced ones. The predicted stereoselective modes are discussed in line with experimental observations. It is demonstrated that the “symmetry-disfavored” reactions inferred from the usual cycloaddition mechanism can be interpreted as the concerted cross-bicyclization reactions.
  • Nobuaki Washida, Gen Inoue, Hajime Akimoto, Michio Okuda
    1978 Volume 51 Issue 8 Pages 2215-2221
    Published: 1978
    Released: April 19, 2006
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    The factor F, the number of NO molecules which are converted photochemically into NO2 when one hydrocarbon molecule is consumed, was determined for fourteen different hydrocarbons in the photochemical oxidation process. Experiments were carried out in a 67 dm3 Pyrex reaction chamber in which a mixture of hydrocarbon, NO, H2O, and air was irradiated by a xenon short arc lamp. In the range from low to middle conversion, hydrocarbons and NO decayed nearly exponentially, NO being converted into NO2. The observed value of F was approximately two for most of the hydrocarbons studied. The value is in line with the long chain mechanism involving OH radicals predicted by Heicklen et al. Only m-xylene gave a larger F value. Reaction sequences of the long chain mechanism caused by OH radicals were discussed, a generalized kinetic model for the chain mechanism being proposed. This will be useful for the atmospheric modeling of photochemical smog.
  • Nobuko Kanehisa, Kenichi Onuma, Shinzo Uda, Kiyoshi Hirabayashi, Yasus ...
    1978 Volume 51 Issue 8 Pages 2222-2233
    Published: 1978
    Released: April 19, 2006
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    X-Ray crystal structure analyses of three (acetylacetonato)organoantimony(V) compounds have been conducted. Crystals of [(acac)MeSbCl3] belong to the tetragonal system: a=13.865(1), c=24.935(5) Å, space group I41/a with Z=16. [(acac)Me2SbBr2] forms monoclinic crystals: a=9.247(1), b=7.695(1), c=9.104(1) Å, β=106.94(1)°, space group P21/m with Z=2. Crystals of [(acac)Ph2SbCl2] (high-melting point form) belong to the monoclinic system: a=14.733(11), b=7.541(1), c=16.014(13) Å, β=92.66(1)°, space group P21/c with Z=4. All structures have been elucidated by the heavy atom method and refined by the block-diagonal least-squares procedure. Through the three compounds, the antimony atoms have a slightly distorted octahedral geometry with substituents on apical positions, slightly bent towards the planar acetylacetonato groups.
  • Kazuo Fueki, Yasumasa Ouchi
    1978 Volume 51 Issue 8 Pages 2234-2236
    Published: 1978
    Released: April 19, 2006
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    The solubility and diffusion coefficient of sulfur in copper were determined by a new method, wherein a thin copper(I) sulfide film was formed on the surface of a copper specimen and the decrement of its thickness after diffusion annealing was determined coulometrically. It was found that the solubility Cs could be represented by
    logCs(ppm)=−0.616−0.410(104T),
    and the diffusion coefficient is given by
    D=0.834×exp(−40900⁄RT)cm2s−1.
  • Kazuko Oyanagi, Kozo Kuchitsu
    1978 Volume 51 Issue 8 Pages 2237-2242
    Published: 1978
    Released: April 19, 2006
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    The bond distances (rg) and angles (rα) in ethyl methyl ether have been determined by gas electron diffraction as follows: average of C(methyl)–O and C(methylene)–O=1.418±0.002 Å, C–C=1.520±0.004 Å, C–H=1.118±0.004 Å, ∠C–O–C=111.9±0.5°, ∠O–C–C=109.4±0.3°, ∠H–C–H=109.0±0.4°, where uncertainties represent estimated limits of experimental error. The two rg(C–O) distances have been estimated independently with the aid of the rotational constants for the trans conformer reported by Hayashi et al.: C(methyl)–O=1.413±0.009 Å and C(methylene)–O=1.422±0.007 Å. The dihedral angle for the gauche conformer, 84±6°, and the relative abundance of the trans and gauche conformers in the gas phase at 20 °C, nt⁄(nt+ng)=0.80±0.08, have also been determined.
  • Kazuko Oyanagi, Kozo Kuchitsu
    1978 Volume 51 Issue 8 Pages 2243-2248
    Published: 1978
    Released: April 19, 2006
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    The bond distances (rg) and angles (rα structure) in ethyl methyl sulfide have been determined by gas electron diffraction as follows: average of C(methyl)–S and C(methylenc)–S=1.813±0.004 Å, C–C=1.536±0.008 Å, C–H=1.111±0.008 Å, ∠C–S–C=97.1±1.1°, ∠S–C–C=114.0±0.5°, ∠H–C–H=109.6±1.4°, where uncertainties represent estimated limits of experimental error. The two C–S lengths have been estimated independently with the aid of the rotational constants for the trans conformer reported by Hayashi et al.: C(methyl)–S=1.806±0.027 Å, C(methylene)–S=1.818±0.027 Å. The dihedral angle for the gauche conformer (66±9°) and the relative abundance of the trans and gauche conformers in the gas phase at 20 °C, nt⁄(nt+ng)=0.25±0.15, have also been determined.
  • Yukikazu Hattori, Yoshio Kuge, Shigeru Nakagawa
    1978 Volume 51 Issue 8 Pages 2249-2255
    Published: 1978
    Released: April 19, 2006
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    Relative sensitivities of an electron capture detector (ECD, 63Ni) for aromatic halogeno and nitro compounds were measured at detector temperatures of 230, 290, and 320 °C. The effects of various substituents on the sensitivity of ECD were determined. A good correlation was recognized between the relative sensitivities of ECD and the positions of substituents for aromatic chloro, bromo, and nitro compounds. The plotted logarithm values of ECD sensitivities for aromatic chloro and bromo compounds vs. Hammett’s σ values of various substituents are not linear, but the plots for aromatic nitro compounds follow a straight line. Modified σ values (σH) were determined on the basis of the relative sensitivities of aromatic chloro compounds. Plots of aromatic chloro, bromo, and nitro compounds vs. σH values gave straight lines. The temperature dependence of electron capture coefficients for these compounds was determined using D.C. mode. The electron capture spectra obtained are similar to those using pulsed mode.
  • Isao Oonishi, Shoji Fujisawa, Junji Aoki, Takaaki Danno
    1978 Volume 51 Issue 8 Pages 2256-2260
    Published: 1978
    Released: April 19, 2006
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    It has been shown that the true unit cell of diphenanthro[5,4,3-abcd: 5′,4′,3′-jklm]perylene consists of three subcells in which the atomic arrangements differ slightly from each other. The model for the ordered structure has been deduced from the consideration of weak reflections. The average structure of the subcell with a=30.80, b=3.837, c=19.87 Å, β=112.5°, and Z=4 has been redetermined. The final R value is 0.103 for 1244 independent reflections. The two naphthanthrone planes in the molecule make an angle of 36°, which shows a large distortion from a planar structure.
  • Ryoichi Tsunoda
    1978 Volume 51 Issue 8 Pages 2261-2263
    Published: 1978
    Released: April 19, 2006
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    The Dubinin-Radushkevich plots of active carbons, curved concavely for a high value of log2P0P, on methanol adsorption at 30 °C have been characterized by using a modified Dubinin-Radushkevich equation, i.e.:
    V=CV0exp[−B0A2]exp[A4Δ2⁄2][1−erf(X)]⁄2,
    where erf(X) is the error function, A=RT 1n P0P, V0 is the micropore volume, C is the correcting coefficient for fitting the equation to the experimental data, and X=(A2B0Δ2)Δ⁄\sqrt2, with B0 being the average value of a measure of the micropore size and Δ, the heterogeneity parameter of the micropore size. The significance of the equation was discussed, and it was shown that the equation can describe the heterogeneous micropore systems of active carbons with suitable parameters.
  • Sanae Y. Matsuzaki, Akira Kuboyama
    1978 Volume 51 Issue 8 Pages 2264-2267
    Published: 1978
    Released: April 19, 2006
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    The n,π* absorption and phosphorescence spectra of 1-fluoro-, 2-fluoro, 1-chloro-, 2-chloro-, 1-bromo-, and 2-bromoanthraquinones were studied in solutions, mainly at 77 K. These phosphorescence spectra and their lifetimes resemble those of anthraquinone (AQ), except for those of 1-F-AQ. The phosphorescence spectrum of 1-F-AQ is at longer wavelengths than that of AQ, and its lifetime is 0.8 ms in the methylcyclohexane solution, much shorter than that of AQ. All of the 1-halogenoanthraquinones showed two distinct n,π* singlet-singlet absorption bands at 77 K, and 1-Br-AQ showed an additional band of the n,π* singlet-triplet transition at 492 nm. The low-energy n,π* singlet and triplet states of these compounds are discussed on the basis of these experimental results.
  • Masaru Ichikawa
    1978 Volume 51 Issue 8 Pages 2268-2272
    Published: 1978
    Released: April 19, 2006
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    Methanol synthesis by the catalytic hydrogenation of carbon monoxide proceeded under atmospheric pressure and at 150–250 °C over rhodium, platinum and iridium crystallite catalysts, prepared from well-defined Rh, Pt, and Ir carbonyl cluster compounds highly dispersed on ZnO and MgO. The activity and selectivity of methanol formation depended considerably on the kind of metal carbonyl clusters and metal oxides employed as inorganic carriers. The catalysts prepared by the pyrolysis of smaller Rh, Pt, and Ir carbonyl clusters on ZnO, MgO, CaO, and BeO exhibited a higher selectivity of methanol synthesis. A small amount of ethanol was also produced besides methanol in CO–H2 reaction over the pyrolysed catalysts of Rh carbonyl clusters on MgO, CaO, and BeO. Other metal oxides such as SiO2 gel, γ-Al2O3, SnO2, and WO2 were employed for preparation of the dispersed Rh catalysts from carbonyl clusters, which catalysed mainly formation of methane and higher hydrocarbons with negligible selectivity of the oxygenated products under the reaction conditions.
  • Masaru Ichikawa
    1978 Volume 51 Issue 8 Pages 2273-2277
    Published: 1978
    Released: April 19, 2006
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    Ethanol was catalytically produced in the CO–H2 reaction under atmospheric pressure and at 150–250 °C over rhodium crystallite catalysts prepared from Rh carbonyl cluster compounds highly dispersed on La2O3, TiO2, and ZrO2. The activity and selectivity of ethanol formation depend on the kind of metal carbonyl cluster and metal oxide used as inorganic carriers. The catalysts prepared by the pyrolysis of smaller Rh carbonyl clusters such as Rh2(C5H5)2(CO)3, Rh4(CO)12, and Rh6(CO)16 on La2O3, TiO2, and ZrO2 show higher selectivity of the oxygenated products containing ethanol (main), acetaldehyde, and methanol. The ethanol contents in the oxygenated products increased considerably above 200 °C over the catalysts. CeO2 and ThO2 were also employed in the preparation of the pyrolysed catalysts to disperse the Rh carbonyl clusters, which catalyses the ethanol formation in the CO–H2 reaction at atmospheric pressure.
  • Tooru Taga, Yoshihiro Kuroda, Makoto Ohashi
    1978 Volume 51 Issue 8 Pages 2278-2282
    Published: 1978
    Released: April 19, 2006
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    Lanthanoid-induced 1H NMR shifts of glyceric acid, gluconic acid, and lactobionic acid were observed in D2O. Stoichiometric analysis using the shift data at various pH values indicated that the concentration of a 1 : 1 complex between substrates and lanthanoid ions was higher than that of a 2 : 1 complex at a low pH. The structure of an axially symmetric 1 : 1 complex was obtained on the assumption of a predominant pseudo-contact interaction between a europium ion and the ligand nuclei. All the title glycosidic acids were found to chelate the cation with α-carboxy, α-hydroxy, and β-hydroxy oxygens. The relative position of β-hydroxy oxygen is particularly important for the complex formation between β-hydroxy carboxylic acids and metal ions.
  • Satoshi Inagaki, Yoshio Hirabayashi
    1978 Volume 51 Issue 8 Pages 2283-2288
    Published: 1978
    Released: April 19, 2006
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    The method of electron configuration analysis for many-system interactions (ECAMSI) has been developed and applied to the π electronic structures of polycyclic molecules. The HMO-ECAMSI calculations have been carried out on acenaphthylene, pleiadiene, pyracylene, acepleiadylene, and dipleiadiene. Electron delocalization in the naphthalene core predominates in these molecules and remains unchanged from acenaphthylene to dipleiadiene; the central cross-linked π bond is not a small perturbation. There are four electron-delocalizing modes for the cyclic peripheral conjugation in acepleiadylene which give rise to an additional but appreciable delocalization, while the peripheral delocalization in pyracylene and dipleiadiene is almost completely depressed. The substituent effects on the delocalization have been predicted on the basis of the ECAMSI results and on the concept of the continuity-discontinuity of cyclic conjugation which has recently been developed.
  • Kazushi Arata, Susumu Akutagawa, Kozo Tanabe
    1978 Volume 51 Issue 8 Pages 2289-2293
    Published: 1978
    Released: April 19, 2006
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    The reaction of carvomethene oxide (a mixture of cis- and trans-forms) over solid acids and bases gives trans-and cis-1-methyl-3-isopropyl-1-cyclopentanecarbaldehyde (III), carvomenthone (IV), 1(7)-p-menthen-2-ol of trans-(V) and cis-form and carvotanacetol of trans-(VI) and cis-form. A large amount of III was formed together with IV over SiO2–Al2O3, SiO2–TiO2 and zeolite H-F9. LiClO4, H2SO4/SiO2, FeSO4, and solid H3PO4 gave preferentially IV, while TiO2-ZrO2 formed mainly V and VI. With respect to aluminas, carbonyl compounds (III and IV) were predominantly formed over Al2O3D, while allylic alcohols (V and VI) were preferentially given by Al2O3 A and B.
  • Kiyoshi Hasebe, Janet G. Osteryoung
    1978 Volume 51 Issue 8 Pages 2294-2297
    Published: 1978
    Released: April 19, 2006
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    The pulse polarographic behavior of a new N-nitroso compound, N-nitroso-2-pyrrolidinemethanol, in buffered solutions has been studied. The effects of temperature, mercury pressure, modulation amplitude, surfactant concentration and solvent, and supporting electrolyte have been investigated. The reduction process is complicated and pH-dependent. In acid solutions, N-nitroso-2-pyrrolidinemethanol gives one irreversible reduction wave over a wide pH range below 7. The reduction of the N-nitroso compound is diffusion-controlled in d.c. and of normal pulse polarographic modes. In basic solutions, the reduction is also diffusion-controlled. The 10−7 mol dm−3 content of N-nitroso-2-pyrrolidinemethanol has been determined.
  • Yoshiaki Okajima, Yukiyoshi Aizawa, Yasushi Sugawara
    1978 Volume 51 Issue 8 Pages 2298-2301
    Published: 1978
    Released: April 19, 2006
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    Passive layers on various stainless steels were studied with an ion microanalyzer. An argon ion beam was directed on the specimen surface in an oxygen atmosphere. The use of oxygen atmosphere effectively minimized the difference in ion yields of the elements in the oxidized layers and matrices, making it possible to determine these elements with good reproducibility. 18% Cr–8% Ni and 18% Cr–8% Ni–0.4% Ti stainless steel was exposed to neutral water containing 8 ppm oxygen at 289 °C. The passive layers contained larger amounts of iron and smaller amounts of chromium than the matrices.
  • Yoshitsugu Hasegawa, Yoshimitsu Komiyama
    1978 Volume 51 Issue 8 Pages 2302-2305
    Published: 1978
    Released: April 19, 2006
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    The ion-exchange isotherms for the NH4+–Li+ system on crystalline zirconium phosphate have been determined at 25 °C, and the structural change and water content of the exchanger have also been investigated by means of X-ray diffraction and thermal analysis. The isotherms showed that the ion-exchange reaction took place in one stage, that is, the ammonium-form was converted into the lithium-form in the forward process, and vice versa in the reverse process. However, the results of X-ray diffractometry indicated that the ion-exchange reactions proceeded in three stages in each direction. The isotherms also showed a hysteresis loop. This phenomenon can be ascribed to the difference in the water content of the exchangers, because the X-ray powder patterns of the exchanger phases were essentially identical at similar ionic mole fraction of lithium ion in the exchangers of the two processes.
  • Etsuro Kobayashi
    1978 Volume 51 Issue 8 Pages 2306-2309
    Published: 1978
    Released: April 19, 2006
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    In order to develop an inorganic ion exchanger for industrial use, sulfuric acid has been added to the reaction system of amorphous titanium(IV) phosphate and phosphoric acid. The effects of the additive on the formation of titanium(IV) hydrogenphosphate, a compound observed to have ion exchange affinities towards K+ and Cs+, have been investigated. Ti(HPO4)2·0–1/2H2O has been synthesized using the sulfuric acid solution of TiOSO4, an intermediate in the production process of titanium dioxide. The addition of sulfuric acid to phosphoric acid and a resulting mole ratio of H2SO4/H3PO4 greater than 0.14, produced a borderline in the formation of the monohydrate and hemihydrate within the temperature range of 148–155 °C Titanium(IV) hydrogenphosphate crystallized as fine particles (1–3 μ) by the double decomposition between the sulfuric acid solution of TiOSO4 and phosphoric acid. The X-ray diffraction pattern of the product obtained using the sulfuric acid solution of TiOSO4 above 160 °C compared favourably with that of the hemihydrate already reported. The composition was shown by the formula of Ti(HPO4)2·0–1/2H2O. In the X-ray diffraction pattern of Ti(HPO4)2·0–1/2H2O, two characteristic diffraction lines appeared at 11.6 and 9.21 Å; thus it has been assumed that the product is not a pure crystallite but a mixture of two or more species.
  • Tsugio Sato, Takeshi Suda, Hideki Uchida, Taijiro Okabe
    1978 Volume 51 Issue 8 Pages 2310-2316
    Published: 1978
    Released: April 19, 2006
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    The solubility of hexaamminenickel(II) complexes in aqueous ammonia solution (0 to 37 g-free NH3/100g-solv.) was investigated at temperatures 0–55 °C. It rapidly decreases with increase in free ammonia concentration but increases with rise in temperature. Hexaamminenickel(II) carbonate, sulfate, and chloride are slightly soluble at ammonia concentration above 30 g-free NH3/100 g-solv., but nitrate is considerably soluble even at ammonia concentration of 35 g-free NH3/100 g solv. The thermal decomposition of ammine complexes of nickel(II) was also investigated by means of TG and DTA under a streaming nitrogen gas atmosphere. Ammine complexes of nickel(II) decompose as shown in the following, the reaction orders and activation energies for steps a, b, c, and d being 0.5, 1.5, 1.0, and 0.5, and 16.5, 38.8, 25.3, and 79.4 kcal/mol, respectively.
    (Remark: Graphics omitted.)
    X-Ray diffraction data for [Ni(NH3)6]Cl2·0.5H2O, [Ni(NH3)6](NO3)2, [Ni(NH3)5]SO4·H2O, and [Ni(NH3)2]SO4 powder are given.
  • Michinori Hiraishi, Shoji Harada, Tatsuya Yasunaga
    1978 Volume 51 Issue 8 Pages 2317-2320
    Published: 1978
    Released: April 19, 2006
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    The pressure-jump method was applied to aqueous solutions of aluminium acetate. Relaxation effects were observed in ms and s regions. Both relaxation times depend a great deal on the pH of solution. They were ascribed to the following complex formation reactions.
    (Remark: Graphics omitted.)
    Detailed studies on the fast relaxation effect revealed that the hydrolyzed ionic species accelerate the overall reaction. The mechanism of the fast reaction was discussed, the kinetic parameters being obtained.
  • Yoshiaki Ito, Shinichi Kawaguchi
    1978 Volume 51 Issue 8 Pages 2321-2326
    Published: 1978
    Released: April 19, 2006
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    Substitution reactions of a nitrite ligand in Co(NO2)4(en or tn) with NH3, py, N3, and NCS have been investigated. The product trinitro complexes were isolated and their geometrical structures were assigned on the basis of NMR data. The preparation method for the two conformational isomers of mer-Co(NO2)3NH3(en) was established. The kinetic data of substitution with azide were analyzed according to the D mechanism. The relative nucleophilicity of ligands towards Co(NO2)3(AA) is in the order: OH>>N3>NO2, CH3COO, NCS>>H2O>Cl, I. Dinitro complexes, [Co(NO2)2(phen)(en or tn)]NO2·H2O and K[Co(NO2)2(ox)(tn)] were also prepared.
  • Katsuhiko Kawakami, Masaki Okajima, Toshio Tanaka
    1978 Volume 51 Issue 8 Pages 2327-2329
    Published: 1978
    Released: April 19, 2006
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    The reaction of [RhCl(1,5-C8H12)]2 with the stoichiometric amount of bidentate isocyanide followed by metathesis affords complexes of the types [Rh(L–L)2]PF6 (L–L=CN(CH2)8NC (1), CN(CH2)7NC (2)) and [Rh2(L–L)4](PF6)2 (L–L=CN(CH2)6NC (3), CN(CH2)4NC (4)). The electronic spectra at various concentrations reveal that in dilute solutions 1 and 2 exist as monomers with chelating isocyanides, while 3 and 4 form dimers with bridging isocyanides through intramolecular rhodium–rhodium interactions as the smallest unit. On the other hand, in concentrated solutions 1 and 2 form dimers and 4 tetramers through intermolecular Rh–Rh interactions.
  • Keiko Kamisawa, Keiji Matsumoto, Shun’ichiro Ooi, Hisao Kuroya, ...
    1978 Volume 51 Issue 8 Pages 2330-2333
    Published: 1978
    Released: April 19, 2006
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    The structure of bis(cis-1,3-diaminocyclohexane) palladium(II) chloride has been determined from X-ray diffraction data collected by the counter method. The crystal is orthorhombic with space group Pnnm, a=17.728(5), b=6.418(4), c=6.914(2) Å, and Z=2. The crystal structure has been determined by Patterson and Fourier techniques and refined by a least-squares method to R=0.026 for 1151 independent reflections for which Fo2>3σ(Fo2). The Pd atom has a planar coordination of 4N atoms and the complex cation has a crystallographically imposed C2h symmetry, the two cis-1,3-diaminocyclohexane ligands being related to each other by a two fold axis. The six-membered chelate ring (Remark: Graphics omitted.) is of the envelope conformation. The structural features of the ligating cis-1,3-diaminocyclohexane have been described. The crystal of bis(cis-1,3-diaminocyclohexane)platinum(II) (orthorhombic, a=17.727(8), b=6.371(3), c=6.965(2) Å) was found to be isomorphous with that of the palladium analogue.
  • Naohide Matsumoto, Masahiro Yamashita, Sigeo Kida
    1978 Volume 51 Issue 8 Pages 2334-2337
    Published: 1978
    Released: April 19, 2006
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    A series of deeply colored mixed valence complexes of the general formula [M(AA)2][M′X2(AA)2]Y4 were prepared and characterized, where M–M′=Pt(II)–Pt(IV), Pd(II)–Pt(IV), and Pd(II)–Pd(IV); (AA)=ethylenediamine, propylenediamine, and trimethylenediamine; X=Cl, Br, and I; Y=ClO4, BF4. The relationships between the reflection spectra and the nature of the constituents (X, (AA), Y and M–M′) of the compounds were studied. The value of \barνmax of the main absorption band in the visible region decreases in the order: Cl→Br→I, pn→tn→en, ClO4→BF4, Pd(II)–Pt(IV)→Pt(II)–Pt(IV)→Pd(II)–Pd(IV). On the basis of dichroism of the crystals, it can be predicted that the X–M′(IV)–X…M(II) atoms in these complexes are arrayed in a straight line parallel to the crystal needle.
  • Katsuo Kikuchi, Yuji Maki, Kazuo Sato
    1978 Volume 51 Issue 8 Pages 2338-2341
    Published: 1978
    Released: April 19, 2006
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    The reaction of tropone with aniline, p-toluidine, p-anisidine, and p-chloroaniline in the presence of copper(II) acetate gave 2-arylaminotropones and 2-arylamino-N-aryltroponeimines. However, when o-toluidine and o-anisidine were used, only the corresponding 2-arylaminotropones were obtained. The reaction of tropolone with methylamine, ethylamine, and isopropylamine afforded 3-aminotropolone derivatives, while the reaction with dimethylamine, pyrrolidine, and morpholine gave 3- and 5-aminotropolone derivatives, the latter being minor products.
  • Yasuto Uchio
    1978 Volume 51 Issue 8 Pages 2342-2346
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The essential oil of Chrysanthemum japonense has been analyzed to isolate a new monoterpenoid named nojigiku alcohol together with its acetate, the structure of which has been elucidated as (5R)-2,2-dimethyl-3-methylenebicyclo[2.2.1]heptan-5-ol. In addition, fifteen monoterpenoids including (+)-α-pinene, (+)-camphene, β-pinene, sabinene, 1,8-cineole, p-cymene, filifolone, (+)-chrysanthenone, (+)-camphor, (+)-borneol, (−)-cis-and (+)-trans-chrysanthenyl acetate, cis- and trans-carveyl acetate, (+)-bornyl acetate and nine sesquiterpenoids including α-copaene, β-elemene, β-caryophyllene, germacrene-D, γ-cadinene, calamenene, β-caryophyllene oxide, T-muurolol and α-cadinol were identified in the essential oil.
  • Norihiko Yoneda, Tsuyoshi Fukuhara, Yukio Takahashi, Akira Suzuki
    1978 Volume 51 Issue 8 Pages 2347-2353
    Published: 1978
    Released: April 19, 2006
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    Carboxylation of 2,4,4-trimethyl-1-pentene and 1-octene with carbon monoxide was studied in the presence of various strong acids–H2O–Cu(I) carbonyl catalyst systems in an attempt to find a practical method for the preparation of carboxylic acids. The reaction takes place smoothly at room temperature to give tertiary acids in higher yields than that with the use of sulfuric acid. The procedure is preferable for the ready separation of products from the catalyst layer without quenching by water.
  • Tetsuo Suami, Shigeru Nishiyama, Yasuhide Ishikawa, Eijiro Umemura
    1978 Volume 51 Issue 8 Pages 2354-2357
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    Aminocyclitol antibiotic kanamycin B has been modified as regards the aminocyclitol moiety by removing a hydroxyl group on C-5. 5-Deoxykanamycin B thus obtained was tested against several microorganisms. The structure of 5-deoxykanamycin B was established by mass and 13C NMR spectrometry. 5,6,3′,4′-Tetradeoxyneamine was prepared as a reference compound for 13C NMR spectrometry.
  • Minoru Hirota, Yoshiyuki Takahashi, Motohiro Nishio, Ken Nishihata
    1978 Volume 51 Issue 8 Pages 2358-2360
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    Favored conformations of benzyl t-butyl sulfoxides and their α-methyl derivatives in solutions were determined from their dipole moments and compared with those in crystals.
  • Kenji Inoue, Junya Ide, Kiyoshi Sakai
    1978 Volume 51 Issue 8 Pages 2361-2365
    Published: 1978
    Released: April 19, 2006
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    The key intermediates for 11-methyl- and 11,11-dimethylprostaglandins corresponding to Corey’s lactone were synthesized via the Wittig reaction of dimethyl 2-substituted-4,5-dioxocyclopentane-1,3-dicarboxylate with stable ylides. 11,11-Dimethylprostaglandin E2 was then synthesized.
  • Makoto Ando, Sakae Emoto
    1978 Volume 51 Issue 8 Pages 2366-2368
    Published: 1978
    Released: April 19, 2006
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    The racemization of L-glutamic acid catalyzed by 15 kinds of salicylaldehyde derivatives has been kinetically studied at 25 °C and pH 10 in the presence of copper(II) ion. When 4- and 5-substituted salicylaldehydes were used as the catalyst, Hammett’s plots for the racemization against σ were found to be linear with fewer points deviating from the line than the plots against σ . This fact has not been observed previously, since the salicylaldehyde derivatives tested having a substituent of different value between σ and σ were degraded during the course of reaction at 80 °C. Hammett’s plots for the reaction catalyzed by 3-substituted salicylaldehydes indicated no linear relation with either σ or σ. These catalytic racemizations, including the case of the 6-substituted salicylaldehydes have been discussed.
  • Hisanobu Ogoshi, Hiroshi Sugimoto, Zen-ichi Yoshida
    1978 Volume 51 Issue 8 Pages 2369-2374
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    Absorption, infrared, and 1H-NMR spectra of the ruthenium(II) octaethylporphine carbonyl complex [Ru(II)OEP·CO] were studied in the presence of alkanethiolate anion (SR) as a model system for the reduced cytochrome P-450 carbonyl complex. The 1H-NMR spectra reveal that alkanethiolate anions coordinte toa the central metal atom of Ru(II)OEP·CO as the sixth ligand. The hexaccordinated complex [Ru(II)OEP·CO·SR] has anomalous features as compared with the pentacoordinated complex [Ru(II)OEP·CO]: (1) the Soret band is splitted into two peaks, one in the near UV 363–365 nm region and the other in the 419–428 nm region, (2) the carbonyl stretching frequency is shifted by 25 cm−1 to lower wave number, (3) the proton signals of porphyrin ligand are shifted to higher magnetic field. Similarity of absorption and infrared spectra of the hexacoordinated complex to those of the reduced cytochrome P-450 carbonyl complex supports the axial ligation of the cysteinate to the central iron atom of the heme-proteins. The low wave number shifts of carbonyl stretching vibration and high field shifts of protons in the 1H-NMR spectra suggest the charge transfer interaction from 3p lone pair electrons of sulfur atom of alkanethiolate anion to the central metal and/or the porphyrin ligand.
  • Yoshio Inoue, Yoshiyuki Sasaki, Harukichi Hashimoto
    1978 Volume 51 Issue 8 Pages 2375-2378
    Published: 1978
    Released: April 19, 2006
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    Reaction of carbon dioxide with butadiene catalyzed by palladium–phosphine complexes was studied. When the reaction was carried out in certain polar, aprotic solvents, such as dimethylformamide (DMF), 2-ethylidene-5-hepten-4-olide was formed in about 5% yield by the incorporation of CO2 together with the formation of butadiene linear dimers. The main dimer was 1,3,7-octatriene. The ditertiary phosphines, R2PCH2CH2CH2PR2 where R is methyl or phenyl, were found to be suitable as the ligand for the olide synthesis. A possible mechanism involving the intermediate of π-allyl, σ-allyl form from two moles of butadiene and the palladium complex is proposed.
  • Shô Itô, Isamu Itoh, Yutaka Fujise, Tetsuo Nakatsu, C. A. ...
    1978 Volume 51 Issue 8 Pages 2379-2390
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    Synthesis and solvolytic behavior of derivatives of the highly hindered title compounds are described, exo-Tricyclo[4.4.1.12,5]dodeca-3,7,9-trien-syn-yl tosylate (syn-18-OTs) and the corresponding perhydro derivative, syn-23-OTs, solvolyze at rates that are in reasonable agreement with those predicted by Foote-Schleyer calculations.syn-18-OTs, and its dihydro derivatives, syn-19-OTs and syn-20-OTs, give completely rearranged products on solvolysis in acetic acid and 75% dioxane, 80% acetone, and 75% dioxane, respectively (Table 2). These products can be explained by normal cationic rearrangements, probably occurring after ionization. On the other hand, anti-18-OTs and anti-23-OTs solvolyze at rates ca. 102 times slower than those predicted by Foote-Schleyer calculations. Presumably the anti derivatives of 18-OTs, 20-OTs, 23-OTs, and the tetrahydro tosylate (22-OTs) suffer steric hindrance to ionization. Product formation from anti-18-OTs (Table 3) and anti-19-OTs in acetic acid and 75% dioxane, respectively, is explained as a [3s+3s] sigmatropic shift induced by ionization, with formation of an allylic ion providing the driving force for rearrangement.
  • Isao Kuwajima, Naoki Minami, Toru Abe, Toshio Sato
    1978 Volume 51 Issue 8 Pages 2391-2393
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    1,1-Bis(trimethylsilyl)-1-alkanols were obtained in good yields when ethyl esters of the corresponding carboxylic acids were treated with sodium suspension and chlorotrimethylsilane in refluxing tetrahydrofuran followed by acidic hydrolysis.
  • Kenji Fujinuma, Yoji Hashida, Kohji Matsui
    1978 Volume 51 Issue 8 Pages 2394-2397
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    2-Azido-4,6-dimethoxy-1,3,5-triazine (1a) gave an adduct with pyridine in a molar ratio of 1 : 1. On the contrary, 2-azido-4,6-bis(dimethylamino)-1,3,5-triazine (1b) did not react with pyridine. Similarly, 1a gave an adduct with 3-methylpyridine, whereas in the reactions of 1a with 2-methyl-, 4-methyl-, and 2,6-dimethylpyridines, 2-amino-4,6-dimethoxy-1,3,5-triazine was obtained instead of the adduct. On the other hand, 1a and 1b gave the corresponding triazinyliminophosphoranes with triphenylphosphine.
  • Mitsuru Nakayama, Shizuko Eguchi, Shûichi Hayashi, Masao Tsukaya ...
    1978 Volume 51 Issue 8 Pages 2398-2400
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The condensation of 7-benzoyloxy-4′-hydroxyisoflavone with 2-methyl-3-buten-2-ol gave 7-benzoyloxy-4′-hydroxy-3′-(3-methyl-2-butenyl)isoflavone. The hydrolysis of the alkylated isoflavone with dilute alkali afforded neobavaisoflavone [7,4′-dihydroxy-3′-(3-methyl-2-butenyl)isoflavone], which was then converted into isoneobavaisoflavone on heating with formic acid. 7-Benzyloxy-4′-hydroxyisoflavone was condensed with 2-methyl-3-buten-2-ol to give a chroman derivative, which was then converted into isoneobavaisoflavone by hydrolysis. 3′-(3-Methyl-2-butenyl)-5,7,4′-trihydroxyisoflavone was also synthesized from 7-benzoyloxy-5,4′-dihydroxyisoflavone in a similar manner.
  • Noboru Ono, Takashi Yamada, Tadashi Saito, Kazuhiko Tanaka, Aritsune K ...
    1978 Volume 51 Issue 8 Pages 2401-2404
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    A variety of carboxylic acids including simple acids, sterically hindered acids, thermally unstable acids and N-protected amino acids react with alkyl halides in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in benzene to give esters in good yields. The reaction is simple, affording a general method for esterification of carboxylic acids.
  • Hisaji Taniguchi, Eiji Imoto
    1978 Volume 51 Issue 8 Pages 2405-2409
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    When no hydrogen-bonded complex is formed between the precursors (α-chloro-α-hydroxyiminoacetophenone (5a) and α-chloro-α-hydroxyiminoacetone (5b)) of nitrile oxides (phenylglyoxylonitrile oxide (2a) and methylglyoxylonitrile oxide (2b)) and norbornadienes(2,3-bis(methoxycarbonyl)norbornadiene (1) and norbornadiene (6)) in solvents, the exo/endo product ratios for the cycloadditions of 2a and 2b to 1 or 6 increase or decrease with increasing temperature. When the hydrogen-bonded complex between 5a and 1 is formed in a solvent cage, however, the ratio keeps a constant value until the temperature is elevated up to a certain temperature, at which the ratio jumps up. After the jumping, the ratio has another constant value, regardless of the temperature. Similar results are obtained in the cycloaddition of 2b to 1 in the aromatic solvents used.
  • Ippei Nakagawa
    1978 Volume 51 Issue 8 Pages 2410-2414
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    As part of electrochemical studies on tantalum, the electrolytic dissolution and deposition of solid tantalum in molten salt were studies by measuring its overpotentials in a steady state. The measurements were carried out using the dc current polarization technique in the concentration range of 2.00×10−4–2.79×10−1 mole fraction at temperatures between 775 and 875 °C. The kinetic parameters (the exchange current densities, the transfer coefficients, the kinetic averaged valences, and the apparent activation energies) were determined for the anodic and the cathodic reactions in the Tafel region. The over-all reaction was indicated as:
    (m1+m2)Ta2++(2m1−2m2)e\ ightleftarrowsm1Ta0+m2Ta4+
    The Ta2+ ion was previously supposed not to form a complex ion; the Ta4+, however, was a complex ion which decomposed at above 850 °C.
  • Abdu E. Abdel-Rahman, Zarif H. Khalil
    1978 Volume 51 Issue 8 Pages 2415-2418
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    New 1-ethyl-2-[(2-substituted 3-oxoisoindolin-1-ylidene)methyl]-pyridinium or quinolinium iodide merocyanine dyes were obtained by the reaction of 2-methyl quaternary salts with N-substituted phthalimide in the presence of piperidine. 1-Ethyl-2-[(1-substituted 5-oxo-3-pyrrolin-2-ylidene)methyl] quinolinium iodide merocyanines were also prepared. Structural configuration of the synthesised compounds was confirmed by IR and UV spectral determination. 1-Ethyl-2-[[3-oxo-2-(4-phenylthiazol-2-yl)isoindolin-1-ylidene]methyl]quinolinium iodide has high bactericidal activity againsist E.Coli, Staphylococcus Aureus, and Staphylococcus Albas.
  • Kou Hatada, Katsuhiro Fujita, Yoshio Ono
    1978 Volume 51 Issue 8 Pages 2419-2420
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The catalytic activities of Y-zeolites for the synthesis of 1-propylpyrrolidine from tetrahydrofuran and propylamine were examined. Aluminum cation exchanged zeolite was found most active, 65% yield of 1-propylpyrrolidine being attained at 360 °C. The kinetics of the reaction was examined and the reaction mechanism suggested.
  • Yoshiyuki Hirai, Taira Yanagida
    1978 Volume 51 Issue 8 Pages 2421-2422
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The intrinsic viscosities of poly(4-vinylpyridine) (\barMn:1.37×103–9.67×104) were measured by use of various solvents. For every solvent, log[η]-log\barMn plots gave lines with a slope of 1/2 in the region of low molecular weights (\barMn≤104). These lines were parallel to one another. This viscosity behavior was interpreted in terms of the influence of solvents on short-range interactions in the polymer chains.
  • Mahiko Nagao, Yasuhiro Yokota, Tetsuo Morimoto
    1978 Volume 51 Issue 8 Pages 2423-2424
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The pore structure of iron oxides, subjected to oxidation into α-Fe2O3 as well as reduction into Fe3O4, was investigated by means of the t-method. The results show that the reduction is accompanied by the formation of slit-shaped pores, width 14 Å, open at both ends.
  • Katsuma Hiraki, Masayoshi Onishi, Tsuyoshi Ikeda, Kazuko Tomioka, Yayo ...
    1978 Volume 51 Issue 8 Pages 2425-2426
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    New complexes [M(hofl)2(OH2)n] (Hhofl=5-hydroxyflavone; M=Co and Ni, n=2; M=Cu, n=1 and 0) and [M(hofl)3] (M=V and Fe) were synthesized and characterized by IR and electronic absorption spectroscopy. Polynuclear ethoxo(5-hydroxyflavonato)metal(II) complexes of cobalt and copper were also prepared.
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