Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 39 , Issue 8
Showing 1-50 articles out of 54 articles from the selected issue
  • Tokuzo Tonomura, Katsunobu Okamoto
    1966 Volume 39 Issue 8 Pages 1621-1627
    Published: 1966
    Released: March 27, 2006
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    The viscosities, the densities, and the conductivities of aqueous solutions of electrolytes mixed with glycine or with urea have been measured at 15, 25 and 35°C. The relative viscosities and the relative conductivities of the mixed solutions have been expressed by the empirical formulae, η=η′+η0βC and Λ=Λ0(1−γC), respectively. The retarding effect of glycine on the conductivity of the strong electrolytes has been found to be greater than that of urea in the mixed solutions. The states of the hydration of glycine, urea and the strong electrolytes have been discussed on the basis of the relations between B-values in the viscosity formula of Jones and Dole and the effective volumes in aqueous solutions.
  • Ralph J. Tykodi
    1966 Volume 39 Issue 8 Pages 1627-1632
    Published: 1966
    Released: March 27, 2006
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    A sequence of approximate combinatorial treatments of the localized monolayer adsorption of a gas on a lattice of uniform sites with only nearest neighbor interactions allowed generates a one parameter family of isotherm equations. For each of those cases where the general lattice problem has been solved exactly, it is possible to find a value of the adjustable parameter such that critical behavior on the lattice in question is reproduced exactly.
  • Keiji Takeda, Hiroshi Yoshida, Koichiro Hayashi, Seizo Okamura
    1966 Volume 39 Issue 8 Pages 1632-1635
    Published: 1966
    Released: March 27, 2006
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    In order to assertain the polymerization mechanism in the solid state, a solid mixture of propargyl alcohol (monomer), hydrogen peroxide and water was irradiated at −196°C by an ultraviolet light. The structure of the free radicals so formed in the solid medium was then studied by the electron-spin-resonance method. The trapped free radical was a monomer radical, CH≡C–CHOH. This shows that the HO·radicals produced by the photolysis of hydrogen peroxide abstracted the methylenic hydrogen atoms from the alcohol. An examination of the kinetic behavior of free radicals revealed that HO· radicals migrated freely and reacted with monomers at −196°C. The reaction between the monomer radical and HO· radicals is more important than the recombination between monomer radicals.
  • Akira Yokohata, Satoru Tsuda
    1966 Volume 39 Issue 8 Pages 1636-1640
    Published: 1966
    Released: March 27, 2006
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    A study has been made of silent discharge reactions in aqueous solutions of ferrous sulfate and ceric sulfate acidified with sulfuric acid in a hydrogen atmosphere. The present study has confirmed that silent discharge leads to the formation of hydrogen peroxide from water molecules in a dilute sulfuric acid solution, the oxidation of ferrous ions to ferric ions, and the reduction of ceric ions to cerous ions. The same reactions were previously studied in inert gases. A satisfactory interpretation can be made of their mechanisms by taking into consideration the action on the solvent of slow electrons produced in the gaseous phase. In a hydrogen atmosphere, the yields of the foregoing reactions were very small when compared with those in the case of inert gases; however, a good linear correlation was observed between the yield and the duration time of discharge. From these results it has been concluded that the yields can be well interpreted by taking into consideration the action of active species of hydrogen generated in the gaseous phase on the radicals formed from liquid water, besides the action of slow electrons; moreover, the action of active species on the solute cannot be serious. The absorbed dose in the solution was estimated to be approximately 1.9×107 r./hr. from the relation of the dissipated energy calculated electrically to the absorbed dose.
  • Masao Matsui
    1966 Volume 39 Issue 8 Pages 1640-1643
    Published: 1966
    Released: March 27, 2006
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    The radiolysis of a tetrahydrofuran(THF) and furan system was studied at a dose of about 2×1019 eV. ml−1 of 60Co-γ-rays, and the hydrogen which may be formed by the no-ring opening and the carbon monoxide which should be formed by the ring scission were determined. The decrease in the hydrogen yield with an increase fraction of furan was found to be greater than had been expected, while G(CO) fit the expected value. The charge transfer mechanism was presumed for the decrease in the hydrogen yield in the γ-radiolysis of this mixture. Suggestions were made on the probable mechanism of the ring opening of the excited molecule for the formation of carbon monoxide, and on the ionic reaction for hydrogen formation. Furthermore, the probability of the ring scission of the THF molecule was roughly estimated by using the assumed decomposition reaction and the determined G values.
  • Yoshimasa Takezaki, Sadayuki Mori, Hironobu Kawasaki
    1966 Volume 39 Issue 8 Pages 1643-1650
    Published: 1966
    Released: March 27, 2006
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    The gas-phase reaction of dimethyl ether with oxygen atoms produced by the mercury photosensitized decomposition of nitrous oxide has been studied by means of quantitative determinations of the reaction products. Characteristic products are water, methanol, formaldehyde, carbon monoxide, methoxy ethanol and methyl formate. The possible mechanisms of the oxygen attack on the substrate have been considered, and the following steps postulated on the basis of the relative importance of these products and their time variations:
    O+CH3OCH3 –\xrightarrowkE OH+CH3OCH2, OH+CH3OCH3 –→ H2O+CH3OCH2 and CH3OCH2+OH –→ CH3O+CH2OH.
    The rate constant, kE, of the first step has been determined in the competitive reaction with n-butane as:
    kE=6.3×1010exp(−4700/RT) 1. mol−1 sec−1·
  • Takuji Miwa, Masao Koizumi
    1966 Volume 39 Issue 8 Pages 1651-1659
    Published: 1966
    Released: March 27, 2006
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    The quenching action of benzoic acid on the fluorescence of naphthalene derivatives, for instance, N, N-dimethyl-2-naphthylamine, is phenomenologically ascribed to its dimer. In order to examine its molecular mechanism, absorption and fluorescence spectra have been measured on solutions of N, N-dimethyl-2-naphthylamine with and without benzoic acid, using as a solvent cyclohexane to which various amounts of dioxane or ethyl ether has been added. The quenching action of benzoic acid has also been measured in similar solvents. A good parallelism has been found between the change in the absorption spectra of benzoic acid and the change in the quenching action of benzoic acid when both are examined as functions of the concentration of dioxane or ether. From this finding, and from the more precise analysis of the data described in a previous paper (This Bulletin, 38, 529 (1965)), it has been concluded that the quenching action of benzoic acid may be ascribed to the direct interaction between the fluorescer and the benzoic acid dimer. Further, similar quenching actions have been observed in o-, m- and p-toluic acids, and p-methoxy-bonzoic acid.
  • Yoshiki Hayashi, Makoto Kuroda, Akira Inami
    1966 Volume 39 Issue 8 Pages 1660-1670
    Published: 1966
    Released: March 27, 2006
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    The sensitization in photoconductive poly-N-vinylcarbazole was studied systematically. The sensitizers were conveniently divided into two types, optical and chemical. The optical sensitization occurs with a smaller content of a dye, which extends the photoconductivity spectrum to its absorption band. Effective optical (or dye) sensitizers are found to be themselves photoconductive and n-type cationic and to have a slow photoresponse. The chemical sensitization occurs through the formation of a charge transfer complex with a considerable amount of a Lewis acid. The simultaneous addition of optical and chemical sensitizers induces amplified or additive effects; an amplified effect is observed when a strong acid is employed as a chemical sensitizer. A sensitized system with a strong acid shows a very slow photoresponse and may have fairly deep traps which act as a cause of the memory effect.
  • Yoshiki Hayashi, Makoto Kuroda, Akira Inami
    1966 Volume 39 Issue 8 Pages 1670-1673
    Published: 1966
    Released: March 27, 2006
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    The sensitization of the photoconductivity in polyacenaphthylene by a dye and/or a Lewis acid was investigated. The most effective materials are methylene blue (E1⁄2=1500 lux. sec.), rhoda-mine 6G (6000 lux. sec.), and victoria pure blue (6500 lux. sec.) in the dye sensitization, and 1-nitroanthraquinone (1200 lux. sec.), 2, 3-dichloronaphthoquinone (1400 lux. sec.), 1, 5-dichlo-roanthraquinone (1500 lux. sec.), chloranil (1800 lux. sec.), and 2-chloroanthraquinone (1900 lux. sec.) in the Lewis-acid sensitization. The combined effects of a dye and a strong acid were determined in the case of polyacenaphthylene as well as poly-N-vinylcarbazole.
  • Akira Kira, Yoshinori Ikeda, Masao Koizumi
    1966 Volume 39 Issue 8 Pages 1673-1678
    Published: 1966
    Released: March 27, 2006
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    In order to determine the reactive state of acridine when it is photoreduced by ethanol, two types of experiments were undertaken. The first was to study the concentration effect of ethanol on the quantum yield in a benzene solution. These results, however, could not give any unequivocal answer. The second type of experiment was, therefore, made from the standpoint of the triplet energy transfer, using eosine as an energy acceptor for the photoreduction of acridine in an ethanol solution. It was found that, in a deaerated solution, the quantum yield of acridine photoreduction is not affected by the addition of eosine, whereas it was established by the flash technique that, under similar conditions, the energy transfer from the acridine triplet state to eosine occurs at approximately the diffusion-controlled rate. These results lead to the conclusion that the reactive state is not the lowest triplet state.
  • Rudolf Brill, Yoshio Ohsumi
    1966 Volume 39 Issue 8 Pages 1678-1681
    Published: 1966
    Released: March 27, 2006
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    Es wird versucht, Eisenkatalysatoren fur die Ammoniak-Synthese herzustellen, bei denen dem Eisen Fremdmetalle (Chrom, Nickel, Kupfer) zulegiert sind. Um Katalysatoren mit einer Struktur zu erhalten, die der Struktur der aus reinem Eisen hergestellten vergleichbar ist, wurden die Fremdmetalle als solche oder als Oxide dem Carbonyleisen beigemischt, das dann in üblicher Weise durch Schmelzen im Sauerstoffstrom in Magnetit übergeführt wurde. Eine Mischkristall-bildung in der Magnetitphase wurde nur bei Nickel und Chrom gefunden. Durch Reduktion der Spinelle wurde nur bei Nickel eine Legierungsbildung festgestellt. Cr2FeO4 war unter unseren Bedingungen (Reduktion bei 400°C mit Wassersoff-Stickstoff-Gemisch) nicht reduzierbar. Alle mit Kupfer hergestellten Katalysatoren zeigten im reduzierten Zustand Kupfer neben Eisen. Die Legierungskatalysatoren mit Nickel zeigten bei Gehalten bis zu 5% Nickel innerhalb der Fehler-grenze dieselbe Aktivierungsenergie wie reines Eisen, wahrend Katalysatoren mit 10—30% Nickel eine merklich geringere Aktivierungsenergie aufweisen, jedoch tritt dabei ein Kompensationseffekt auf.
  • Ko Kimura, Yoshio Toshiyasu, Ryoichi Fujishiro
    1966 Volume 39 Issue 8 Pages 1681-1683
    Published: 1966
    Released: March 27, 2006
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    The dipole moments of ethylenediamine (N=1), diethylenetriamine (N=2), triethylenetetramine (N=3), and tetraethylenepentamine (N=4) were measured in a benzene solution at 25°C and 45°C. The observed dipole moments of N=1, N=2, N=3, and N=4 are 1.89 D, 2.22 D, 2.37 D, and 2.56 D respectively at 25°C, and 1.84 D, 2.22 D, 2.36 D, and 2.58 D respectively at 45°C. The dipole moments were theoretically calculated on the assumptions that; (i) the dipole moments of these chain molecules are given by the vector sum of the dipole moments of the polar groups of amine, and (ii) all internal rotations about single bonds are free. The calculated values of N=1, N=2, N=3, and N=4 are 1.84 D, 2.15 D, 2.43 D, and 2.68 D respectively. The agreement between the observed values and the calculated values is satisfactory. It may, therefore, be expected that the molecular chains will be in the random coil state. The intramolecular hydrogenbonding is very weak, as there is no temperature dependence of the observed dipole moments.
  • Hiroshi Hagiwara, Etsuro Echigoya
    1966 Volume 39 Issue 8 Pages 1683-1689
    Published: 1966
    Released: March 27, 2006
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    The hydrogen exchange reaction of aniline with deuterium was investigated on supported nickel, cobalt and platinum. The following results were obtained: 1) At 150°C, the hydrogen of the amino group of aniline exchanges at a higher velocity than the hydrogen attached to the benzene ring. At temperatures as high as 300°C, the hydrogen exchange in the benzene ring increases further. 2) The suggested hydrogenation mechanism obtained from the results of the exchange reaction can not be correlated with that obtained from the kinetic study. 3) The catalytic activity for the exchange reaction in the benzene ring is in the order Pt>Co>Ni. 4) The basic oxide support seems to suppress the adsorption of the amino group. 5) The relationship between the adsorption state of the aniline on the catalyst surface and the various reaction products, such as cyclohexylamine, benzene and dicyclohexylamine, has been well established.
  • Masayuki Nakagaki
    1966 Volume 39 Issue 8 Pages 1689-1694
    Published: 1966
    Released: March 27, 2006
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    An application of the double extrapolation method (the Zimm-plot method) for the reduced intensity of light scattered by colloidal dispersions, instead of polymer solutions, is discussed theoretically on the basis of the Mie theory. The correction factor, F, required to recalculate the experimental value of the molecular weight, MR, to the true value, M (M=FMR), is equal to unity in the case of the Rayleigh scattering (α→0) and the Rayleigh-Gans-Debye (R-G-D) scattering (|m–1|→0, where m is the relative refractive index of the sphere to the medium). Usually, however, the value of F is not equal to unity, but is found to be given by an empirical equation F=1–0.155Q+bQ1.5, where Q is a quantity proportional to the reduced specific scattering intensity at θ→0. For the determination of the radius of gyration from the “initial slope,” the R-G-D equation is applicable even in cases where |m–1| is not small. In order to determine the true molecular weight from the molecular weight, Mτ, obtained from the specific turbidity at the infinite dilution, the factor Φ is needed (M=ΦMτ). The factor Φ is considered to be a product; that is, Φ=F\varphi, where the factor \varphi seems to be independent of the m value. The empirical equation obtained was \varphi=1+0.537α2.08
  • V. Zanker, E. Ehrhardt
    1966 Volume 39 Issue 8 Pages 1694-1700
    Published: 1966
    Released: March 27, 2006
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    By ultraviolet spectrometric measurements we studied the photochemical behavior of xanthene, xanthone, 9, 9′-dihydroxydixanthene and dixanthene in aerated and deaerated ethanolic solutions in the range of concentration 5·10−3 M to 10−4 M by Osram-HBO 200- and Hanau TQ 81- lamps. We found: Xanthenes are photostable similar to monoacridans in the absence of oxygen; in the presence of oxygen photooxidation to the corresponding xanthones takes place. The xanthones are photochemically unstable; in oxygen free solvents containing H-atoms, like methanol, ethanol, benzene, cyclohexane, dioxane, they are reduced to xanthenes. In cyclohexane we found a soluble xanthene, 9-cyclohexylxanthydrol. In hexane there is formed a precipitate with a yield above 80%; this is the dimeric xanthene 9, 9′-dihydroxydixanthene. The photo-reaction presumably is going over a diradical, H-atom transfer from the solvent and formation of a xanthydrol monoradical in the primary step and dimerization to the 9, 9′-dihydroxydixanthene. Irradiation of solutions of xanthone and xanthene in benzene furnish 9-hydroxydixanthene. Solutions of equal molarity of xanthone and acridan yield under irradiation also a solid photoproduct; this is 9, 9′-diacridan. The first step of reaction is photoreduction, where xanthene tranfers a H-atom to xanthone and the hydroxyxanthyl radical dimerizes with the xanthyl radical or the acridanyl radical dimerizes with themselves and forms the diacridan.
  • Yoshihisa Suzuki, Nobuya Nagashima
    1966 Volume 39 Issue 8 Pages 1701-1705
    Published: 1966
    Released: March 27, 2006
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    A new molecular compound, which consists of L-glutamic acid, L-pyroglutamic acid and water of crystallization in a 1 : 1 : 1 mole ratio, has been discovered. In its crystal, the unit-cell is monoclinic with a=5.10, b=7.20, c=18.38 Å, and β=96.6°C, and the space group has been determined to be P21. Equilibrium measurements in the system of L-glutamic acid, L-pyroglutamic acid and water at 20°C, 30°C, and 50°C, showed that the transition temperature from the molecular compound to L-pyroglutamic acid and α-form L-glutamic acid is 35.5°C, while that to L-pyroglutamic acid and β-form L-glutamic acid is 20.5°C. Thus, the molecular compound is stable only below this temperature. This molecular compound has an incongruent solubility. When it is placed in water, a crystallization of L-glutamic acid takes place as the molecular compound is dissolved. A similar molecular compound consisting of D-glutamic acid and D-pyroglutamic acid is also obtained, but no molecular compound of the L-glutamic acid and D-pyroglutamic acid, or vice versa, is obtainable. On the basis of these facts, an optical resolution is actually possible for glutamic acid. When this molecular compound is heated, it is converted into another molecular compound at about 70°C due to the loss of the water of crystallization; then it is decomposed to L-glutamic acid (β-form) and L-pyroglutamic acid at about 90°C.
  • Shin Suzuki, Yasushi Inoue
    1966 Volume 39 Issue 8 Pages 1705-1715
    Published: 1966
    Released: March 27, 2006
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    Studies of the chemical behavior of protactinium(V) were carried out with the TTA-benzene extraction method, the ion exchange method and the filtration method. When the protactinium concentration is less than 10−6 M and the perchloric acid concentration is 0.3—2.0 N, the reaction of TTA extraction may proceed as:
    PaOm(OH)n5−2mn+4HT\ ightleftarrowsPa(OH)T4+(m+n−1)H2O+(5−2mn)H+
    where 2m+n is 3 and 4, or as:
    PaOm(OH)nT4−2mn+4HT\ ightleftarrowsPaT5+(m+n)H2O+(4−2mn)H+
    where 2m+n is 2 and 3.
    The cation exchange experiment gives results consistent with this conclusion. On the other hand, when the concentration of protactinium is higher than 10−6 M, the above relation does not hold, even in the 5 N perchloric acid solution, because protactinium forms the aggregates to a great extent. This has been confirmed by the filtration experiment.
  • Kuwako Ohkawa, Jinsai Hidaka, Yoichi Shimura
    1966 Volume 39 Issue 8 Pages 1715-1720
    Published: 1966
    Released: March 27, 2006
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    Two new mixed cyano complexes, cis-[CoCl(CN)en2]Cl (red) and cis-[CoBr(CN)en2]Br (deep rose), have been synthesized and resolved into their optical isomers. The splitting patterns of the ligand field absorption bands of the cis and the trans isomers of the halogenocyanobis(ethylenediamine)cobalt(III) ion have been discussed in relation to the geometrical configurations of the complexes and to the σ- and π-antibonding contribution of the cyanide or the halide ligands to the metal d-orbitals. These studies have been made successfully using the circular dichroism data of the optically active cis-[CoX(CN)en2]X (X=Cl, Br).
  • Hajime Ishii, Hisahiko Einaga
    1966 Volume 39 Issue 8 Pages 1721-1724
    Published: 1966
    Released: March 27, 2006
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    It has been found that Calcichrome forms a stable complex with aluminum; the reaction has been studied spectrophotometrically in order to find the optimum conditions for the determination of aluminum. The aluminum-Calcichrome complex is formed gradually at about pH 6; its composition has been found to be 1 to 1. The complex has two absorption maxima, at approximately 312 and 560 mμ, when measured against water. On the other hand, two absorption maxima were found, at approximately 317 and 620 mμ, in the curve obtained as the difference between Calcichrome and its aluminum complex. A linear relationship was noticed between the concentration of aluminum and the absorbance under the conditions recommended. The molar extinction coefficients of the complex at 317 and 620 mμ were 11500 and 7200. and the sensitivities were 2.3×10−3 and 3.7×10−3 μg. Al/cm2 respectively, which correspond to log(I0I)=0.001. Some other metals, such as copper(II), iron(III), titanium(IV), vanadium(V), and zirconium(IV), interfere with the determination.
  • Otohiko Tsuge, Kiyoshi Yanagi, Sh\={o}ji Fukuhara
    1966 Volume 39 Issue 8 Pages 1724-1729
    Published: 1966
    Released: March 27, 2006
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    Methods for the preparation of cis-, trans-1, 2-diphthalimidoethylene, its nitro derivative, 1,1-diphthalimido- and 1, 2-bis(o-sulfobenzimido)ethylene are described. In this connection, the thermal, irradiated and iodine-catalyzed isomerization of cis- and trans-1, 2-diphthalimidoethylene have also been studied in detail.
  • Sadao Yoshikawa, Oh-Kil Kim
    1966 Volume 39 Issue 8 Pages 1729-1733
    Published: 1966
    Released: March 27, 2006
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    The amino ester hydrolysis by polymeric sulfonic acids increased as the concentration ratio, Cester/Cacid, was lowered, and a maximum in the plot of the rate constant, k, against the Cester/Cacid ratio was attained near the ratio=0.4 in the case of the β-alanine methyl ester as well as in the case of γ-methyl L-glutamate. At this optimum concentration, the catalytic effect of polyvinylsulfonic acid (A), for example, in the hydrolysis of the β-alanine methyl ester was 16 times greater than that of hydrochloric acid, while the effect of polystyrenesulfonic acid was about 7 times greater. The catalytic effects of hydrochloric acid and ethanesulfonic acid were the same in all cases, and there was no such specific behavior as in the former. Furthermore, the catalytic efficiency of polyvinylsulfonic acid in amino ester hydrolysis increased with an increase in the polymer molecular weight, in contrast with the case of the carboxylic ester, while no such correlation was found in the polystyrenesulfonic acid. Besides, the catalytic effect of partially-neutralized polymeric sulfonic acid, polyvinylsulfonic acid especially, decreased remarkably with the degree of neutralization. These different kinds of behavior can be interpreted as being due to the difference in the expansion in solutions and in the geometrical distances between nearest-neighboring sulfonic acid groups on the polymer chain.
  • Shunsuke Murahashi, Heimei Yuki, Koichi Kosai
    1966 Volume 39 Issue 8 Pages 1734-1738
    Published: 1966
    Released: March 27, 2006
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    A number of methods of preparation were studied in an attempt to synthesize 5-vinyl-hydantoin using acrolein as a starting material. There were three possible routes: 1) the thermal decomposition of 5-(9,10-dihydroanthracene-9,10-endo-α, β-ethyl)-hydantoin at 400°C; 2) that of 5-(2-acetoxyethyl)-hydantoin and 3) the elimination reaction of dimethyl 2-(5-hydantoin)-ethyl sulfonium iodide in dimethyl sulfoxide by potassium t-butoxide. However, all the reactions gave 5-ethylidene-hydantoin as the product instead of 5-vinyl-hydantoin. An extreme ease of isomerization from 5-vinyl-hydantoin to 5-ethylidene-hydantoin was caused by the highly stable structure of the latter compound. The strong resonance stabilization of 5-ethylidene-hydantoin was observed in the ultraviolet spectrum. 5-Methyl-5-vinyl-hydantoin, which has no migrating hydrogen, could not be obtained from the 5-methyl derivatives of the above compounds.
  • Motonori Ohno, Tetsuo Kato, Satoru Makisumi, Nobuo Izumiya
    1966 Volume 39 Issue 8 Pages 1738-1747
    Published: 1966
    Released: March 27, 2006
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    The synthesis of a cyclic decapeptide, cyclo-L-phenylalanyl-D-phenylalanyl-L-asparaginyl-L-glutaminyl-L-tyrosyl-L-valyl-L-ornithyl-L-leucyl-D-phenylalanyl-L-prolyl, which has an amino acid sequence determined by Craig et al. for natural antibiotics, tyrocidine A, has been described. The chemical and biological properties of the synthetic product have been shown to be in agreement with those of the natural tyrocidine A.
  • Haruhiko Aoyagi, Nobuo Izumiya
    1966 Volume 39 Issue 8 Pages 1747-1753
    Published: 1966
    Released: March 27, 2006
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    A cyclic decapeptide dihydrochloride cyclo-(L-valyl-L-ornithyl-L-leucyl-D-phenylalanylsarcosyl)2·2HCl, which is an analog of gramicidin S and a cyclic pentapeptide monohydrochloride cyclo-L-valyl-L-ornithyl-L-leucyl-D-phenylalanylsarcosyl·HCl, were synthesized for the purpose of comparing their antibacterial activities with gramicidin S. The cyclic decapeptide dihydrochloride was obtained by hydrogenolysis in the presence of hydrogen chloride of a cyclic benzyloxycarbonyl-substituted decapeptide, which had been prepared by the cyclization of a corresponding linear decapeptide active ester. The cyclization reaction of a linear pentapeptide active ester yielded a mixture of a cyclic benzyloxycarbonyl-substituted pentapeptide as a major component, and a cyclic decapeptide and an unidentified cyclic peptide as minor components. The effects of two cyclic peptide hydrochlorides on bacterial growth were tested. The cyclic decapeptide was as active as gramicidin S; however, the cyclic pentapeptide showed no activity in relation to any of the microorganisms tested.
  • Heinosuke Yasuda, Hiroshi Midorikawa
    1966 Volume 39 Issue 8 Pages 1754-1759
    Published: 1966
    Released: March 27, 2006
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    Substituted 2-hydroxybenzaldehydes react with two equivalents of ethyl cyanoacetate to give α-β-(substituted 3-coumarinyl)-β-cyano-β-ethoxycarbonylethylenes in the presence of piperidine. When equivalent aldehyde and the cyanoacetate are used, substituted 2-imino-3-ethoxycarbonyl-2H-chromenes result, without the isolation of arylidenecyanoacetates. In o-hydroxyaryls, salicylic and o-thymotinic aldehydes, which give benzopyrane derivatives, are exceptional cases. 5-Phenylazo- and 5-nitro-2-hydroxybenzaldehydes result in the formation of coumarin derivatives. An abnormal condensation is also shown in the cases of 3, 5-dibromo-2, 4-dihydroxy-, 2-hydroxy-3-methoxy- and 2-hydroxy-4-methoxybenzaldehydes; i. e., the first one yields a 1:1-condensation product, while the last two give 3-cyanocoumarin derivatives, even with an excess of ethyl cyanoacetate. The condensation of m- and p-hydroxybenzaldehydes with ethyl cyanoacetate give the normally-expected arylidenecyanoacetates, even in the presence of a large excess of the cyanoacetate.
  • Juji Yoshimura, Masuo Funabashi, Sadao Ishige, Tetsuo Sato
    1966 Volume 39 Issue 8 Pages 1760-1764
    Published: 1966
    Released: March 27, 2006
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    As a part of the investigation of the stabilities of the esters between N-acetyl-D-glucosamine and various amino acids, N-acetyl-3-O- and 4-O-aminoacyl-D-glucosamines were synthesized. Benzyl N-acetyl-4, 6-O-benzylidene-α- and -β-D-glucosaminide, and benzyl N-acetyl-3-O-benzyl-6-O-trityl-α- and -β-D-glucosaminide were condensed with N-benzyloxycarbonyl-amino acids by the dicyclohexylcarbodiimide method, followed by the step-by-step removal of the protecting groups. The α-Glycosidic benzyl group, however, could not be removed by the catalytic hydrogenolysis in the presence of oxalic acid, probably because of a steric hindrance.
  • Takanobu Kumamoto, Takenori Nagaoka, Teruaki Mukaiyama
    1966 Volume 39 Issue 8 Pages 1765-1767
    Published: 1966
    Released: March 27, 2006
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    The reaction of 2-cyclohexylimino-3-cyclohexyl-4, 5-diphenyl-4-oxazoline with isocyanate or isothiocyanate was studied. When the oxazoline was treated with isocyanate, an exchange reaction took place, thus forming new 2-imino-oxazoline and cyclohexyl isocyanate. Similarly, the reaction of the oxazoline with carbon disulfide resulted in the formation of 3-cyclohexyl-4, 5-diphenyl-4-oxazoline-2-thione and cyclohexyl isothiocyanate. Further, cyclohexyl isothiocyanate was obtained by the reaction of dicyclohexylcarbodiimide or cyclohexyl isocyanate with carbon disulfide.
  • Ryotaro Kotani
    1966 Volume 39 Issue 8 Pages 1767-1773
    Published: 1966
    Released: March 27, 2006
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    The pyrolysis of cyclohexanemethyl methanesulfonate and 1-methylcyclohexanemethyl p-toluenesulfonate has been investigated, yielding predominantly rearranged cycloalkenes, with lesser amounts of cycloalkanes. The experiments support the suggestion that the pyrolysis may proceed, at least in part, through a free radical process. The methanesulfonic ester, on acetolysis in a 50% aqueous acetic acid solution, gave rearranged-unrearranged cycloalkenes and alcohols, and an unrearranged acetate, whereas the p-toluenesulfonic ester gave exclusively rearranged cycloalkenes, alcohols and acetates.
  • Hirokichi Harada, Noriyoshi Sakabe, Yoshimasa Hirata, Yujir\={o} Tomii ...
    1966 Volume 39 Issue 8 Pages 1773-1775
    Published: 1966
    Released: March 27, 2006
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    The structure of dihydroteleocidin B monobromoacetate, the derivative of a toxic substance teleocidin B produced by some streptomyces, has been determined by X-ray analysis. Crystals of the derivative, C30H44O3N3Br, are orthorhombic (a=14.50, b=26.60, c=7.93Å, z=4, the space group is P212121). The intensities of 2053 reflections were measured using CuKα radiation. The bromine position was determined by Patterson methods, and all the carbon, oxygen and nitrogen atoms were elucidated by three-dimensional minimum function methods. A three-dimensional Fourier synthesis and the least squares methods completed the refinement, giving a final R value of 16.4%. The derivative has a substituted indole nucleus with a nine-membered lactum ring.
  • Juji Yoshimura, Hachiro Komoto, Hiroaki Ando, Toshio Nakagawa
    1966 Volume 39 Issue 8 Pages 1775-1778
    Published: 1966
    Released: March 27, 2006
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    2,7-Dideoxy-L-manno-heptose was synthesized from 1-C-nitro-1,7-dideoxy-L-glycero-L-talo-heptitol by the elimination of the C-2 hydroxyl group (nitroolefin formation), by hydrogenation and by the Nef reaction. The corresponding ethyl α-glycoside, its acetate, and a few related 1-amino-1-deoxy derivatives were also described.
  • Michio Kobayashi, Koichi Honda
    1966 Volume 39 Issue 8 Pages 1778-1782
    Published: 1966
    Released: March 27, 2006
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    N-Sulfinylaniline reacted with nitrogen tetroxide to form the anhydrous benzenediazonium nitrate. The reactions of N-sulfinylaniline and several of its p-substituted derivatives with nitrosyl chloride also gave the anhydrous diazonium chlorides in the crystalline state. Aliphatic N-sulfinyl-amines reacted with nitrosyl chloride to form alkyl chlorides, probably by the decomposition of the initially-formed diazonium chlorides; during this reaction, no rearrangement of the alkyl group was observed.
  • Michio Kobayashi, Reiko Kiritani
    1966 Volume 39 Issue 8 Pages 1782-1784
    Published: 1966
    Released: March 27, 2006
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    Sodium benzoate-18O reacts with methyl chlorosulfite to give methyl benzoate-18O ina low yield; the excess 18O content has been found to be exactly one-half of that in the starting benzoic acid. Another reaction of the labeled benzoic acid with phenyl chlorosulfite gives phenyl benzoate-18O; its excess 18O atom% is also one-half of that of benzoic acid. Both reactions are considered to proceed by way of the intermediate formation of the benzoic sulfurous mixed anhydrides, the decomposition of which by acyl-oxygen splitting affords the carboxylic esters labeled only in the carbonyl group.
  • Michio Kobayashi, Akira Yabe, Reiko Kiritani
    1966 Volume 39 Issue 8 Pages 1785-1787
    Published: 1966
    Released: March 27, 2006
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    The reactions of the cyclic sulfites with aldehydes to give the cyclic acetals have been investigated with the stereochemical and with the 18O tracer technique. Both groups of evidence have indicated that the bonds broken are the S–O, not the C–O bond, of the sulfites.
  • Michio Kobayashi, Nobuko Koga
    1966 Volume 39 Issue 8 Pages 1788-1791
    Published: 1966
    Released: March 27, 2006
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    The ultraviolet spectra of several substituted benzenesulfinic acids and their ethyl esters have been recorded, and the assignments of the absorption have been disucssed briefly.
  • Yukio Mizutani, Keiichi Yamamoto, Seishiro Matsuoka
    1966 Volume 39 Issue 8 Pages 1792-1795
    Published: 1966
    Released: March 27, 2006
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    The thermal degradation of polypropylene was investigated in the presence of the fine powdery polymer with crosslinkage by the use of an extruder under a nitrogen atmosphere. The fine powdery polymer was thus found to be effective as an accelerator for the thermal degradation of polypropylene. The fine powdery polymer used was prepared by the emulsion polymerization of some vinyl monomers and divinyl benzene or by the polymerization of glycidyl methacrylate and divinyl benzene in n-heptane. The fine powdery polymer consisting of glycidyl methacrylate and divinyl benzene was preferable to that with no reactive functional group, because of the reactivity of the glycidyl group. The polypropylene was modified and made dyeable by the thermal degradation accelerated by the fine powdery polymer.
  • Motoo Saga, Toshiyuki Shono, Koichiro Shinra
    1966 Volume 39 Issue 8 Pages 1795-1800
    Published: 1966
    Released: March 27, 2006
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    Dibasic acids containing a pyromellitimide ring were synthesized by the reaction of pyromel-litic dianhydride with such ω-aminoacids as glycine, ε-amino-caproic acid and p-amino-benzoic acid. By the condensation polymerization of the dibasic acids obtained above with diamines, polypyromellitimide-amides were synthesized. The polymers were soluble in m-cresol and sulfuric acid, and the inherent viscosities of the polymers ranged from 0.21 to 0.42 (in m-cresol). The polymers were found to be considerably heat-stable.
  • Hiroshi Hagiwara, Eiichi Kojima, Etsuro Echigoya
    1966 Volume 39 Issue 8 Pages 1800-1806
    Published: 1966
    Released: March 27, 2006
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    The kinetics of the catalytic hydrogenation of aniline with a cobalt-alumina catalyst in the temperature range from 160° to 210°C was studied by a differential flow reactor with a fixed bed. (1) The rate of reaction reaches a maximum in the 180–190°C range for the hydrogenation of aniline. From the thermodynamic calculations and the experimental results for a fluidized-bed reactor, the reverse reaction was found to be almost negligible below 200°C under the conditions of the reaction. This phenomenon was explained by the proposed kinetics of the reaction. (2) The initial rate of reaction without cyclohexylamine, and the rate when some cyclohexylamine was added to the reactants, were measured at atmospheric pressure over the following range of conditions of partial pressures; hydrogen 0.3–0.92 atm., aniline 0.05–0.2 atm., cyclohexylamine 0–0.24 atm. It was concluded that a plausible rate-controlling step was the surface reaction, i. e., the reaction between the adsorbed aniline and hydrogen on the surface of the catalyst. The equation for the vapor phase hydrogenation of aniline on a cobalt-alumina catalyst in the temperature range from 150°C to 210°C was determined to be:
    r=k\fracKH3KAPH3PA(1+KHPH+KAPA+KCPC)4
  • Kensuke Shima, Hiroshi Sakurai
    1966 Volume 39 Issue 8 Pages 1806-1808
    Published: 1966
    Released: March 27, 2006
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  • Hiroko Hoshino, Nobuhide Wasada, Toshikazu Tsuchiya
    1966 Volume 39 Issue 8 Pages 1809
    Published: 1966
    Released: March 27, 2006
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  • Hiroyuki Yoshida
    1966 Volume 39 Issue 8 Pages 1810-1811
    Published: 1966
    Released: March 27, 2006
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  • Shoichi Matsumoto
    1966 Volume 39 Issue 8 Pages 1811-1813
    Published: 1966
    Released: March 27, 2006
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  • Kôzô Sone, Shunji Utsuno
    1966 Volume 39 Issue 8 Pages 1813-1814
    Published: 1966
    Released: March 27, 2006
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  • Akihiro Kagemoto, Sachio Murakami, Ryoichi Fujishiro
    1966 Volume 39 Issue 8 Pages 1814-1815
    Published: 1966
    Released: March 27, 2006
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  • Shin-ichi Sasaki, Hung Cheh Chiang, Kazuo Habaguchi, Hong-Yen Hsü ...
    1966 Volume 39 Issue 8 Pages 1816-1817
    Published: 1966
    Released: March 27, 2006
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  • Susumu Tatsumi, Masami Imaida, Yoshiharu Izumi
    1966 Volume 39 Issue 8 Pages 1818-1819
    Published: 1966
    Released: March 27, 2006
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  • Hideki Sakurai, Kenji Tominaga, Makoto Kumada
    1966 Volume 39 Issue 8 Pages 1820
    Published: 1966
    Released: March 27, 2006
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  • Pang-bu Hong, Kenkichi Sonogashira, Nobue Hagihara
    1966 Volume 39 Issue 8 Pages 1821
    Published: 1966
    Released: March 27, 2006
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  • Akira Misono, Yasuzo Uchida, Kunikazu Yamada
    1966 Volume 39 Issue 8 Pages 1822
    Published: 1966
    Released: March 27, 2006
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  • Rokuro Okawara, Kiyoshi Yasuda, Masanobu Inoue
    1966 Volume 39 Issue 8 Pages 1823
    Published: 1966
    Released: March 27, 2006
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  • Tamotsu Tominaga, Yoshinobu Odaira, Shigeru Tsutsumi
    1966 Volume 39 Issue 8 Pages 1824
    Published: 1966
    Released: March 27, 2006
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