Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 40 , Issue 12
Showing 1-50 articles out of 71 articles from the selected issue
  • Koji Nobutoki, Hiroshi Sumitomo
    1967 Volume 40 Issue 12 Pages 2725-2730
    Published: 1967
    Released: March 27, 2006
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    Four kinds of complexes were prepared by the reactions of benzil with a potassium or potassium-sodium alloy in tetrahydrofuran. The polymerizations of styrene (St), isoprene (Ip), methyl methacrylate (MMA), and ε-caprolactone (CL) initiated with these complexes were attempted. St and Ip were found to be polymerized by the dipotassium or tetrapotassium adducts of benzil, but not by the monopotassium ketyl. All these complexes were effective in polymerizing MMA and CL. A new class of multi-chain copolymers with different kinds of branches was also prepared by the polymerizations of MMA and CL with the potassium adducts of polystyrene ketones synthesized by the coupling reactions of one-ended living polystyrene with 2, 4′-dichlorobenzophenone or terephthaloyl chloride.
  • Kazuo Mukai, Hiroaki Nishiguchi, Kazuhiko Ishizu, Yasuo Deguchi, Hideo ...
    1967 Volume 40 Issue 12 Pages 2731-2739
    Published: 1967
    Released: March 27, 2006
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    The electron spin resonance spectra of 2,6-di-t-butyl-4-methylphenoxyl (I) and 2,4,6-tri-t butylphenoxyl (II) have been observed under high resolution, and it has been shown experimentally that the para methyl proton hyperfine splitting (aCH3H) in the radical (I) increases, while, inversely, the meta proton hyperfine interaction decreases, as the dipole moment of the solvent (μ) increases. The relationship between these two variables can be written as:
    asolv)=asolv=0)+K·μsolv,
    where μsolv is the dipole moment of the solvent and where K is the constant of proportionality. Further study of diphenyl nitric oxide (DPNO) (IV) and di-p-anisyl nitric oxide (DPANO) (V) radicals has shown this to be a general form of the solvent effect. However, in the case of various kinds of solvents with OH or NH groups, it has been found that aN deviates from the equation. This phenomenon has been explained qualitatively by the effect of hydrogen bonding. Therefore, the variation in the coupling constants has generally been explained by two effects, that is, the μ dependence described above and the electron delocalization arising from hydrogen bonding. Similar experiments performed with 2,4,6-tri-t-butylphenoxy (II) and 2,4,6-tri-t-butylanilino (III) radicals have shown that the variation in the hyperfine splitting constants is small because of the steric hindrance of tertiary butyl groups in these molecules.
  • Kiyoshi Arakawa, Nobuo Takenaka
    1967 Volume 40 Issue 12 Pages 2739-2742
    Published: 1967
    Released: March 27, 2006
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    An ultrasonic investigation of aqueous solutions of urea was made by means of the pulse technique. The ultrasonic velocity and absorption were measured on solutions of about 14– 43 wt% in the frequency range from 5 to 45 Mc/sec. In an 8 M urea solution the velocity vs. the temperature curve was found to be horizontal in the temperature range from 20 to 40°C. The α/f2vs. logf curves (α, absorption coefficient; f, frequency) showed a very small frequency dependence throughout this experiment. The magnitude of α⁄f2 first decreases upon the addition of urea; at about 4–6 M of urea it reaches a shallow minimum, thereafter slowly increasing. At about 8 M of urea the contribution to the ultrasonic relaxation from the open-packed structure in water completely disappears, and the contribution from the water-urea structure as well as that from the association of urea is small.
  • Hiroko Shimada, Yoshiya Kanda
    1967 Volume 40 Issue 12 Pages 2742-2748
    Published: 1967
    Released: March 27, 2006
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    The matrix elements of the spin-orbit interaction and the intensities of the T←S transitions resulting from possible perturbing processes in glyoxal and its halogen substituted derivatives are examined. The calculated results show that the T←S transitions in these molecules borrow their intensities predominantly from the 1Bu(π,π*)←1Ag and 3Bg(n*)←3Au transitions by means of the first-order spin-orbit interaction. An experimental study of the T←S absorptions of haloderivatives of glyoxal shows that the intensity increases with an increase in the atomic number of the halogen atom. This intensification due to halosubstitution can be interpreted in terms of two factors; (1) the halosubstitutional effects on the transition energies and on the intensities of these two perturbing transitions, and also on the transition energy of the T←S transition, and (2) the halosubstitutional effect on the matrix element of the spin-orbit interaction, which comes to involve the one-center term on the halogen atom if slight delocalizations of the n-orbital as well as of the π-orbital over the halogen atom are taken into account.
  • Shoichi Matsumoto
    1967 Volume 40 Issue 12 Pages 2749-2753
    Published: 1967
    Released: March 27, 2006
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    Two kinds of unusual behavior in the temperature dependence of electrical conductivity has been observed. One is the anomaly that the resistance begins to increase remarkably with the rise in the temperature around 64°C; the other is a bending-phenomenon in the linear temperature-dependence of the resistance about 54°C. The observed activation energies for conduction are 3.0–3.3 eV below and 4.5–4.8 eV above the anomaly, the energies of which are almost compatible with the intrinsic band-gap energies for conduction, 3.5 and 4.6 eV, estimated, respectively, from the optical absorption and from the values of the ionization potential and the electron affinity. As for below the bending-phenomenon, the observed activation energy is 1.4–1.6 eV, which is quite small compared with the intrinsic band-gap energies estimated. The anomaly beginning around 64°C is interpreted as due to the crystal-phase transition of a higher-order at 60–70°C; the remarkable increase in resistance may be connected with the changes in the intermolecular interaction in the crystal due to the rearrangement of molecules caused by the phase transition. The bending-phenomenon at about 54°C seems to be attributable to an impurity-effect by oxygen.
  • Masamoto Iwaizumi, Masayasu Suzuki, Taro Isobe, Hiroshi Azumi
    1967 Volume 40 Issue 12 Pages 2754-2760
    Published: 1967
    Released: March 27, 2006
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    Ion pairs formed by alkali metals with acenaphthene in ether-type solvents have been investigated by means of electron spin resonance (ESR). The ESR spectra of the ion pairs were found to show phenomena quite analogous to those found by de Boer et al. in the pyracene-alkali ion system; similar two-line-width alternation effects were also observed in the present work. These observations were contrary to the expectations formed by a consideration of the pyracenealkali metal ion pair, where the phenomena have been explained on the basis of the assumption that a potential well exists near the two ethylene bridges. This paper shows that, in the acenaphthene-alkali metal ion pairs, the alkali ion may be situated above the naphthalene skeleton rather than near the ethylene bridge. One of the line-width alternation effects is explained in terms of the exchange reaction between two ion-pair conformations in which the alkali ion is situated above and under the molecular plane respectively, while the other is ascribed to the oscillation of the cation in the potential well above either side of the molecular plane.
  • Hiroshi Kato, Hideyuki Konishi, Hiroko Yamabe, Teijiro Yonezawa
    1967 Volume 40 Issue 12 Pages 2761-2767
    Published: 1967
    Released: March 27, 2006
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    Using a semi-empirical ASMO SGF method for all valence electron systems, but a method modified to include one-center exchange integrals and an off-diagonal core integral as estimated by the approximation in our previous treatment, the electronic structures of trans- and cis-isomers of butadiene, acrolein, and glyoxal are calculated. The energy sequence of the molecular orbitals, the charge distributions in lone-pair orbitals and π MO’s, and the charge distribution in these compounds are investigated. The n–π* and π–π* transition energies are also presented; the agreement between the calculated and observed values is almost entirely satisfactory. Further, the singlet-triplet oscillator strength in the trans-glyoxal is estimated by means of the obtained results.
  • Toshio Uchijima, Masamichi Takahashi, Yukio Yoneda
    1967 Volume 40 Issue 12 Pages 2767-2772
    Published: 1967
    Released: March 27, 2006
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    The method for the determination of the surface excess oxygen of oxides has been provided by using aqueous hydrazine solution as a reducing reagent and applied to several pure and lithium doped nickel oxide catalysts, calcined at various temperatures from 350 to 900°C. Two different kinds of procedures, i. e., titration of the amount of hydrazine consumed and volumetric measurement of gaseous nitrogen evolved, have been employed. A satisfactory agreement is obtained between both methods, which affirms that the following reaction is taking place.
    N2H4+2O(S)→N2+2H2O
    The amount of the surface excess oxygen decreases monotonously with increasing calcination temperature and also with increasing concentration of the lithium oxide additives. From comparison of these results with those due to acidic chloride and iodide methods, most of the excess oxygen is concluded to exist on the surface of the oxides and, furthermore, a certain distribution in the oxidation power of the excess oxygen is suggested to exist.
  • Tsunehiko Nakagawa, Setsuo Takamuku, Hiroshi Sakurai
    1967 Volume 40 Issue 12 Pages 2773-2776
    Published: 1967
    Released: March 27, 2006
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    In the γ-radiolysis of 1,4-cyclohexadiene vapor at room temperature, the contribution of neutral and ionic intermediates to the main products has been investigated by the application of electric fields and by the addition of nitrous oxide and ammonia as an electron and an ion scavenger respectively. It was suggested that the precursors of hydrogen, acetylene and 1,3-butadiene are exclusively the neutral excited molecules of 1,4-cyclohexadiene directly produced by the γ-irradiation, while those of the C6 products and polymer are mostly the ionic species. It was further derived that the contribution of neutralization reaction has little importance in the formation of hydrogen, acetylene and 1, 3-butadiene.
  • Masamitsu Tanimura, Toshio Mizushima, Yukio Kinoshita
    1967 Volume 40 Issue 12 Pages 2777-2779
    Published: 1967
    Released: March 27, 2006
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    The crystal structure of dichlorobis(cyclohexanone oxime)palladium, PdCl2(C6H10NOH)2, has been determined from three-dimensional X-ray photographic data. The crystals belong to the triclinic space group P\bar1, with these cell parameters: a=8.81 Å, b=9.99 Å, c=4.99 Å; α=91°32′, β=99°41′ and γ=102°02′. The unit cell contains one molecule of the complex. The palladium atoms are spaced at intervals of 4.99 Å along the c-axis and have a square planar coordination, with two chlorine atoms at 2.24 Å and two nitrogen atoms of the oxime group at 2.08 Å. The complexes are hydrogen-bonded with each other in strings of indefinite length along the c-axis, and the hydrogen bond distance between the oxygen atom of the hydroxyimino group and the chlorine atom is 2.93 Å.
  • Yoshiyuki Kiso, Mitsue Kobayashi, Yoshinori Kitaoka, Keizo Kawamoto, J ...
    1967 Volume 40 Issue 12 Pages 2779-2787
    Published: 1967
    Released: March 27, 2006
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    A series of phenylphosphorus compounds, such as triphenylphosphine, triphenylphosphine oxide, triphenylphosphite, diphenylphosphite, tricresylphosphite, monophenylphosphate, triphenylphosphate, phenylphosphonic acid and phenylphosphonous acid, were irradiated in a nuclear reactor for 15–2100 min with a thermal neutron flux of 5×1012 n/cm2/sec. The relative amounts of the 32P-labeled gaseous products and the products soluble in an aqueous solution in the irradiated samples were then estimated. It was found that the compounds containing an oxygen atom bonded as P=O in a molecule had a tendency to yield the higher percentages of the products which were nonvolatile and soluble in an aqueous solution. The recoil products were separated into components by paper chromatography, and the chemical form of each component was identified. It was shown that the number of recoil products separated and the distribution of the chemical forms were greatly influenced by the chemical forms of the target compounds. The chemical reactions of the recoil 32P atom are also discussed, and a mechanism of the reactions which fits the experimental results is proposed.
  • Kenichi Fukui, Hiroshi Fujimoto
    1967 Volume 40 Issue 12 Pages 2787-2792
    Published: 1967
    Released: March 27, 2006
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    The sum of one-electron energies in the extended Hückel MO theory has been related to the total energy in the LCAO SCF MO theory including electron repulsion and nuclear repulsion terms. The sum of one-electron energies in the extended Hückel MO theory can be divided into the two parts; one almost independent of nuclear configuration and one highly sensitive to the configurational change. Of these the latter is found to be responsible for the stabilization energy due to the bond formation. The role of the highest occupied MO and the lowest unoccupied MO toward chemical reaction has been also discussed in the framework of the extended Hückel calculations. The partial AO population in these particular MO’s is shown to be almost valence-inactive one, being ready to be mobilized in case of chemical interaction with other systems.
  • Takaaki Danno, Takashi Kajiwara, Hiroo Inokuchi
    1967 Volume 40 Issue 12 Pages 2793-2795
    Published: 1967
    Released: March 27, 2006
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    The forced resonance vibration method was applied to several needle-like organic crystals, triphenylene (I), 1,2,3,4-dibenzanthracene (II), coronene (III), anthracene-trinitrobenzene (TNB) complex (IV), perylene-TNB (V), coronene-TNB (VI), acridine-iode (VII), and acetyl-acetone-Gu (VIII), and their elastic constants were obtained. The observed Young’s moduli, E1 of these organic crystals were E1(I)=1.19×1010 dyn/cm2, E1(II)=2.81×1010, E1(III)=1.10×1010, E1(IV)=1.24×1011(V)=7.77×1010, E1(VI)=9.99×1010, E1(VII)=1.67×1011 and E1(VIII)=2.87×1010 dyn/cm2. These values are consistent with the E1-values of some aromatic hydrocarbons, as obtained from the acoustic velocity.
  • Kyoji Shinsaka, Shoji Shida
    1967 Volume 40 Issue 12 Pages 2796-2800
    Published: 1967
    Released: March 27, 2006
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    The effects of added N2O, NO, N2O-NO mixture and NH3 on the yields of fragment products of n-hexane in the γ-radiolysis of liquid n-hexane at 40°C have been investigated. All of these additives decrease to a certain extent the G-values of fragment products. The decreases of the G-values at sufficiently high N2O concentration (∼0.3 mol/l) are approximately the same as those in the presence of NH3. The degrees of contribution of neutralization process and other processes to the C-C bond rupture have been separately estimated from the decreases at sufficiently high concentration of N2O, NO and N2O-NO mixture. It is shown that processes other than neutralization may play rather an important role than neutralization in the C-C bond rupture. The effect of added NH3 on the yields of fragment products of n-hexane may be attributable to either the proton transfer from n-C6H14+ to NH3 or the charge transfer from n-C6H14+ to NH3.
  • D. Singh, Anirudh Mishra
    1967 Volume 40 Issue 12 Pages 2801-2806
    Published: 1967
    Released: March 27, 2006
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    The conductance of lithium bromide in acetone-water mixtures has been measured at different temperatures (25–40°C) in the dielectric constant range from 17.80 to 61. The association constants and centre-to-centre cation-anion distances have been calculated by a modified Fuoss-Onsager equation applicable to 2<b<15, where b is the Bjerrum parameter. The increase in ion size and the decrease in association constants with the addition of water have been interpreted in terms of the solvated dipoles which contain both solvent molecules in the sheath of solvation. The variation in Walden products and in association constants with the change in the composition of the solvent and the temperature is well represented on this model.
  • Tsunenobu Shigematsu, Masayuki Tabushi, Masakazu Matsui, Takaharu Honj ...
    1967 Volume 40 Issue 12 Pages 2807-2812
    Published: 1967
    Released: March 27, 2006
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    The synergistic effects of n-hexyl alcohol, TBP and TOPO on the extraction of rare earth ions with benzoyltrifluoroacetone in benzene have been studied. The stability constants of the adducts were determined by means of the curve-fitting method. The equation based on the shift of pH1⁄2 (−ΔpH1⁄2) was also employed to analyse the data. The results were discussed in relation to the ionic radius of rare earth elements and summarized as follows: (1) The stability of rare earth benzoyltrifluoroacetonate decreases but that of the adducts increases, as the ionic radius increases. (2) The maximum number of base molecules bonding to one molecule of the metal chelate is 2, except that in the case of lutetium adduct with TOPO, where the formation of secondary adducts is not observed. (3) Although the overall stability constant of the adduct increases in the following order; lutetium < terbium < europium < lanthanum, as mentioned above, the first stability constant does not show such a distinct sequence. Therefore the contribution of the second stability constant seems to be an important factor. (4) Organic bases studied form stable adducts with rare earth benzoyltrifluoroacetonates in the following order; n-hexyl alcohol<TBP<TOPO. This order corresponds to the donating power of lone pair electrons of the oxygen atoms in these compounds.
  • Mutsukazu Kamo, Yoshimasa Takashima, Shigeru Ohashi
    1967 Volume 40 Issue 12 Pages 2812-2815
    Published: 1967
    Released: March 27, 2006
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    The Mössbauer spectra of three iron - sodium metaphosphate systems have been studied. The bonding characteristics of the iron atom with the phosphates have been discussed from the results of the Mössbauer spectra. The data for the fused iron oxide - sodium metaphosphate system suggest that the bonding of the iron atom with the phosphates is considerably ionic and the arrangements of metaphosphates in these systems are at random and in a tangle. Some informations on the structure of the Fe2(OH)(PO3)5 system were described.
  • Haruo Miyata
    1967 Volume 40 Issue 12 Pages 2815-2818
    Published: 1967
    Released: March 27, 2006
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    2-(1, 8-Dihydroxy-3, 6-disulfo-2-naphthylazo)-mandelic acid forms a stable violet complex with thorium ion at 1:1 molar ratio in an acidic solution. The acid dissociation constants of the reagent and the apparent stability constant of its thorium complex were estimated spectrophotometrically at 25°C and μ=0.1. It was found that the thorium complex formed by the present reagent was more stable than those of the other phenyl-azo-chromotropic acid derivatives reported in the preceding papers.
  • Akira Ouchi, Mitsutoshi Hyodo, Yoshiaki Takahashi
    1967 Volume 40 Issue 12 Pages 2819-2822
    Published: 1967
    Released: March 27, 2006
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    Derivatives of acetylacetonato-nickel(II) in which the coordinating oxygen is replaced by sulfur to various extents have been isolated by the reaction between nickel(II) acetylacetonate and hydrogen sulfide in an ethanolic solution, using hydrogen chloride as the catalyst. These compounds are soluble in organic solvents, such as benzene, acetone, or carbon tetrachloride, but can hardly be dissolved in water. The proton magnetic resonance spectra indicate that the proton of the methyl group attached to the C=S carbon gives greater chemical shifts than that of the methyl group attached to the C=O carbon. The infrared spectra of these compounds are discussed with particular reference to the C=S stretching bands. The electronic spectra of these compounds and the Hückel LCAO-MO calculation of bis dithio compounds are also compared.
  • Toshikazu Mitsuji
    1967 Volume 40 Issue 12 Pages 2822-2825
    Published: 1967
    Released: March 27, 2006
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    The separation of Pa(IV) and Pa(V) was investigated using various co-precipitants which were insoluble in acidic solutions. Among them, thorium fluoride was found to be the most useful co-precipitant. The conditions for the separation of both valency states of protactinium were also investigated in detail. This method was applicable to protactinium solutions in the concentration range down to tracer level. It was difficult to reduce Pa(V) completely on a tracer scale by means of a liquid zinc amalgam. When Cr(III) was added to the system, however, the complete reduction of 233Pa(V) was readily attained. The role of Cr(III) was considered to be that Cr(II) formed by liquid-zinc-amalgam reduction mediates the reduction of Pa(V) and protects Pa(IV) from re-oxidation. By this method tetravalent protactinium in a perchloric acid medium was also confirmed to be very stable.
  • Akitsugu Nakahara, Kazuko Hamada, Isao Miyachi, Ken-ichi Sakurai
    1967 Volume 40 Issue 12 Pages 2826-2829
    Published: 1967
    Released: March 27, 2006
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    The reactions of copper(II) chelates of β-diketones such as acetylacetone, benzoylacetone, dibenzoylmethane and benzoylacetaldehyde and of chelates of their related compounds such as salicylaldehyde and 2-hydroxyacetophenone with glycine or glycylglycine were investigated. Only bis(salicylaldehydato)copper(II) and bis(benzoylacetaldehydato)copper(II) reacted with glycine to form the respective glycinato-Schiff base complexes, whereas the other chelates did not react with glycine under the same condition. On the other hand, all the chelates except bis(dibenzoylmethanato)copper(II) reacted with glycylglycine to form the respective glycylglycinato-Schiff base complexes. The reaction at pH 4.5 between bis(salicylaldehydato)copper(II) and triglycine resulted in the hydrolytic cleavage of peptide bond, producing the salicylideneglycylglycinatocuprate(II) and free glycine. As the results of this investigation, five new copper(II) chelates were synthesized and characterized.
  • Kuwako Ohkawa, Jinsai Hidaka, Yoichi Shimura
    1967 Volume 40 Issue 12 Pages 2830-2835
    Published: 1967
    Released: March 27, 2006
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    Five new cis isomers of the [Co(X)(CN)en2]n+ complexes, namely, those of X=NH3, OH2, OH, I and NO2, have been prepared and resolved into their optically active isomers. A new trans isomer of X=NO2 has also been prepared. The splitting of the d→d absorption bands of the geometrical isomers of the [Co(X)(CN)en2]n+ complexes have been discussed in reference to their visible and ultraviolet absorption spectra, rotatory dispersion and circular dichroism spectra.
  • Toshiki Wakabayashi
    1967 Volume 40 Issue 12 Pages 2836-2839
    Published: 1967
    Released: March 27, 2006
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    The distribution coefficients of oxine between aqueous solutions with the ionic strength of 0.1 and 12 inert solvents were determined photometrically at 25°C. By a previously-proposed equation, the distribution coefficients were then correlated quantitatively with the solubility parameters of the solvents. The solubility parameter for oxine was evaluated as 10.9, and that for an aqueous solution, as 16.95, while the molar volume of oxine was estimated to be 124 cc/mol. The distribution of the two methyl derivatives of oxine was also discussed.
  • Nobuyuki Tanaka, Yumiko Kobayashi, Minoru Kamada
    1967 Volume 40 Issue 12 Pages 2839-2843
    Published: 1967
    Released: March 27, 2006
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    The optical density of charge transfer spectra of some tervalent substitution-inert complex cations in an ultraviolet region increases by the addition of halide and sulfate ions. From the change in optical density the association constants were determined at ionic strength 0.07 (NaClO4) and 25°C. The values are 2.2±0.5 for Co(NH3)63+Cl, 2.2±0.6 for Co(NH3)63+Br, 0.71±0.5 for Co(NH3)63+ I, 114±3 for Co(NH3)63+SO42−, 2.9±0.5 for Co(en)33+ Cl and 102±8 for Co(en)33+SO42− respectively. The difference of these values from the reported values are related to the method for the measurements. Absorption maxima of the third absorption bands are obtained at 196 mμ for Co(NH3)63+ and at 210 mμ for Co(en)33+.
  • Takao Takaya, Hataaki Yoshimoto, Eiji Imoto
    1967 Volume 40 Issue 12 Pages 2844-2849
    Published: 1967
    Released: March 27, 2006
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    Three Convenient syntheses of cis-1, 2-ureylenecyclopentane (VI) and cis-cis-3-methyl- 1, 2-ureylenecyclopentane (VIa), from 2-carbethoxycyclopentanone (I) and 5-methyl-2-carbethoxycyclopentanone (Ia) respectively, are described. The Curtius degradation of cis-2-aminocyclopentanecarboxylic acid derivatives took place without cis-trans isomerization. The hydrogenation of ethyl 3-methyl-2-ureidocyclopent-1-ene-1-carboxylate at 70°C gave two isomeric products, the major (IIIa), cis-cis-, and the minor (IIIb), cis-trans-3-methyl-2-ureido-1-carbethoxycyclopentane.
  • Masaharu Yoshikawa, Tetsuya Kato
    1967 Volume 40 Issue 12 Pages 2849-2853
    Published: 1967
    Released: March 27, 2006
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    5′-Nucleotides could be conveniently prepared in high yields by the phosphorylation of 2′, 3′-O-isopropylidene nucleosides with phosphoryl chloride in the absence of any organic solvent. The rate of phosphorylation in a large excess of phosphoryl chloride was markedly promoted by the partial hydrolysis of phosphoryl chloride with a small amount of water. The undesirable cleavage of the glycosidic linkage in nucleoside, which was observed particularly in a strongly acidic medium caused by the addition of excessive water, could be suppressed by the addition of ethers or amines in a phosphoryl chloride solution. 2′, 3′-O-Isopropylidene derivatives of adenosine, inosine, and guanosine gave the corresponding 5′-nucleotides in good yields, whereas that of xanthosine reacted very slowly, unlike the above nucleosides. All attempts at the phosphorylation of 2′, 3′-O-isopropylidene-2-mercaptoinosine were unsuccessful. The influence of substituents at the 2-position in purine bases on phosphorylation was investigated by comparing the reactivity between the above-mentioned nucleosides and their methylated derivatives, such as 2-dimethylaminoinosine, 2-methoxyinosine, and 2-methylthioinosine; it was found that these methylated nucleosides were readily phosphorylated to give the corresponding 5′-nucleotides in nearly quantitative yields.
  • Kentaro Anzai, Saburo Suzuki
    1967 Volume 40 Issue 12 Pages 2854-2859
    Published: 1967
    Released: March 27, 2006
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    Dimethyl sulfoxide (DMSO) and acetyl chloride reacted with 2-benzimidazolinethione (I), converting the latter compound to its thiomethoxymethyl and methylenebis derivatives. From the reaction mixture the following compounds were isolated: 1, 3-dithiomethoxymethyl-2-benzimidazolinethione (VII), 1, 1′-methylenebis-3-thiomethoxymethyl-2-benzimidazolinethione (VIII), 1-thiomethoxymethyl-2-benzimidazolinethione (IX), 1, 1′-methylenebis-2-benzimidazolinethione (XIII), and 2-(methylenesulfonium)benzimidazolide (XIV). The mechanism for the formation of these compounds will be discussed. The reaction of 2-benzoxazolinethione (XX) with DMSO and acetyl chloride yielded, besides its thiomethoxymethyl and methylenebis derivatives, 1-hydroxymethylbenzoxazolone (XXIII); the mechanism for the exchange of the sulfur in XX with the oxygen will also be discussed. N-Alkyl derivatives of I could be distinguished from S-alkyl derivatives by their ultraviolet spectra.
  • Shizunobu Hashimoto, Junzo Sunamoto, Katsuhiko Sato
    1967 Volume 40 Issue 12 Pages 2860-2866
    Published: 1967
    Released: March 27, 2006
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    The autocatalytic reactions of the aqueous monosulfide to the aqueous disulfide by an ultraviolet light, oxygen, and sodium m-nitrobenzene sulfonate have been investigated. The rate of the disulfide formation by the photo-oxidation of the aqueous monosulfide was given by the following equation: d(S22−)/dt=k0(S2−)2/(S2−)02. Also in the reaction of aromatic nitro compound and aqueous monosulfide, the disulfide formation was observed prior to the amine formation. On the basis of the results obtained, the mechanisms of the alkaline sulfide reduction of aromatic nitro compounds have been discussed.
  • Shizunobu Hashimoto, Junzo Sunamoto, Akira Aoki
    1967 Volume 40 Issue 12 Pages 2867-2871
    Published: 1967
    Released: March 27, 2006
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    The ESR techniques were used in order to examine the presence of the radical species in the alkaline sulfide reduction of aromatic nitro compounds and in the photooxidation of an aqueous monosulfide solution. The ESR spectra were clear when observed by ultraviolet-light irradiation on an aqueous monosulfide solution: they were the signals of a singlet, with a g-value of 2.002±0.001 and a maximum slope width of 3.1 gauss, and a doublet, with a g-value of 2.00±0.001 and a coupling constant of 114 gauss. The singlet was identified as the signal of the sulfide ion radical, S·, while it was most reasonable to assume the doublet to be signals due to the interaction of the sulfide ion radical with the hydrosulfide or the hydroxide in the solution. On the other hand, ESR spectra were also observed in the reaction of sodium m-nitrobenzene sulfonate with an aqueous monosulfide solution; these spectra were identical with the sulfide ion radical and the radical-anion of the nitro compound. On the basis of the results obtained, we have discussed the mechanisms of the alkaline sulfide reduction of aromatic nitro compounds and these reduction intermediates.
  • Sadayoshi Satsumabayashi, Shinichi Motoki
    1967 Volume 40 Issue 12 Pages 2872-2874
    Published: 1967
    Released: March 27, 2006
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    The reactions of β-cyanoacrolein or its dimethyl acetal were investigated. Various new compounds were prepared by the application of several basic reactions, namely, oxidation, reduction, addition, and others. Moreover, β-cyanoacrolein was found to react as a dienophile or as a diene in Diels-Alder reactions. In the reaction with butadiene, isoprene, and 1, 3-pentadiene, cyanotetrahydrobenzaldehyde derivatives were obtained. When ethyl vinyl ether or butyl vinyl ether was used as a dienophile, dihydropyran derivatives were prepared; this pyran was hydrolyzed with dilute hydrochloric acid to 2-cyanoglutar aldehyde.
  • Akira Misono, Tetsuo Osa, Seiichiro Koda
    1967 Volume 40 Issue 12 Pages 2875-2884
    Published: 1967
    Released: March 27, 2006
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    The present authors previously reported a method of synthesizing nitriles from aldehydes by using iodine as an oxidant (Bull. Chem. Soc. Japan, 39, 854 (1966)). The possible route and detailed conditions of this reaction have now been investigated in the case of benzaldehyde; the results will be described in this paper. Benzaldehyde, ammonia, and iodine in methanol react to form benzonitrile and methyl benzoate as the main products. A possible reaction mechanism is suggested by a consideration of the effect of the temperature and of the concentrations of the reactants, and of the effect of the addition of ammonium iodide and water, as well as by a consideration of the results of the reaction starting from hydrobenzamide. The mechanism may be as follows. Iodamine, which is in equilibrium with iodine and ammonia, oxidizes benzilideneimine, which arises from the reaction between benzaldehyde and ammonia to give hydrobenzamide, to produce benzonitrile. Methyl benzoate is produced by the oxidation of the hemiacetal which arises from the reaction between benzaldehyde and methanol. Gyaphenin (2, 4, 6-triphenyl-1, 3, 5-triazine) is found as a by-product, but it is shown not to be produced by the trimerization of benzonitrile.
  • Susumu Toki, Hiroshi Sakurai
    1967 Volume 40 Issue 12 Pages 2885-2889
    Published: 1967
    Released: March 27, 2006
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    The photoreaction of benzophenone with furan was studied kinetically in a benzene solution. A reaction mechanism was proposed, and the rate constants of elementary reactions were determined. Benzophenone gives primarily oxetane with furan through the n* lowest triplet state. Benzophenone reacts with the oxetane initially formed to afford a 2 : 1-adduct or to decompose that to the starting materials. The ratio of the addition to the decomposition is 1 : 4. The simplest scheme for the direct cycloaddition of a benzophenone triplet and an alternate scheme involving a biradical intermediate are discussed; the second scheme is more acceptable. The rate of the formation of the intermediate is considerably slower in a benzophenone-furan system than in a benzophenone-ketenimine system (ca. 1/10). The formation of oxetane is greatly dependent on the ratio of the bond-forming to the bond-breaking of the biradical intermediates, which are efficiently formed (4.2×107 M−1 sec−1 for furan and 4.0×107 M−1 sec−1 for oxetane).
  • Rume Sakai, Shoichi Ikeda, Toshizo Isemura
    1967 Volume 40 Issue 12 Pages 2890-2894
    Published: 1967
    Released: March 27, 2006
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    The soluble collagen was extracted from chicken leg tendon with a 0.15 M citrate buffer at pH 3.8. The denaturation temperature was estimated to be 38°C by measuring the intrinsic viscosity and also by measuring the optical rotation at 589 mμ. The optical rotatory dispersion constants (λc) of collagen and gelatin were found to be 210±10 and 220±10mμ respectively. The intrinsic viscosity of collagen was 12.5±1.0 dl/g. The rotational diffusion coefficient at 20°C in water was 795±75 sec−1. The sedimentation constant at 20°C in water was 3.0S. From these data, the size and molecular weight of collagen were discussed. The collagen of chicken leg tendon is 2900 to 3000 Å in length and 12 to 16 Å in diameter, and has a molecular weight of 34×104.
  • Chuji Aso, Toyoki Kunitake, Yoshikazu Ishimoto
    1967 Volume 40 Issue 12 Pages 2894-2899
    Published: 1967
    Released: March 27, 2006
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    Cyclopentadiene was found to polymerize as its thiourea complex when irradiated with γ-rays from 60Co. The conditions of preparing the complex were an important factor in increasing the conversion, the use of 50 vol% aqueous acetone giving the best results. The polymer yield increased with dose and with temperature. The apparent activation energy of the polymerization was 2.7 kcal/mol. The poly cyclopentadiene thus obtained was concluded from its NMR and IR spectral data to have mainly the 1,4-structure.
  • Kazuhiko Onuma, Keisuke Wada, Junzo Yamashita, Harukichi Hashimoto
    1967 Volume 40 Issue 12 Pages 2900-2903
    Published: 1967
    Released: March 27, 2006
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    A kinetic study has been made of the cobalt acetate-catalyzed decomposition of t-butyl hydroperoxide in acetic acid at 40.4°C, and the effects of added lithium salts on the decomposition rate have been studied. The observed rate law for the cobalt acetate-catalyzed decomposition is: v=k2[Co(II)][t-C4H9OOH]+k3[Co(II)]2[t-C4H9OOH]. When lithium halides (chloride and bromide) are added to this system, the cobalt acetate is changed to cobaltous halide and the rate of decomposition is markedly decreased. In the case of lithium bromide the hydroperoxide decomposition is accompanied by the generation of molecular bromine. The mechanisms for the bromine formation will be discussed. The role of these cobalt salts in the course of autoxidation in relation to the hydroperoxide decomposition will also be discussed.
  • Michinori Waki, Okitoshi Abe, Reiko Okawa, Tetsuo Kato, Satoru Makisum ...
    1967 Volume 40 Issue 12 Pages 2904-2909
    Published: 1967
    Released: March 27, 2006
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    To investigate the contribution for the antibacterial activity of the ornithine residues in gramicidin S, two analogs of gramicidin S, [2, 2′-L-α,γ-diaminobutyric acid]- and [2, 2′-lysine]-gramicidin S, were synthesized by the cyclization reaction of linear pentapeptide active esters with pyridine. It was indicated that the crude product of the cyclization of each of the linear active esters was composed of two components. The protected cyclic decapeptide, a less soluble material, was easily isolated by fractional crystallization, and the hydrogenolysis of this product in the presence of hydrogen chloride afforded the crystalline hydrochloride of [2, 2′-diaminobutyric acid]-or [2, 2′-lysine]-gramicidin S. These cyclic decapeptides were as active as natural gramicidin S; the results indicated that the side chains of the ornithines in gramicidin S could be replaced by other chains without a loss of activity.
  • Noboru Sugiyama, Makoto Yamamoto, Tadao Takano, Choji Kashima
    1967 Volume 40 Issue 12 Pages 2909-2913
    Published: 1967
    Released: March 27, 2006
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    2-Acetoxy-l, 3-dicarbonyl compounds were synthesized by two methods, one consisting of the condensation of 1, 3-dicarbonyl compounds with an electrophilic reagent, followed by acetoxylation. By this method three new compounds, ethyl 5-phenyl-2-acetoxy-3-oxopentanoate (XVII), ethyl 5, 5-diphenyl-5-hydroxy-2-acetoxy-3-oxopentanoate (XVIII), and ethyl 2-acetoxy-3-oxoheptanoate (XIX), were obtained. The other method consisted of the acetoxylation of 1, 3-dicarbonyl compounds, followed by condensation. By this method three other new compounds, 6-phenyl-6-hydroxy-3-acetoxy-2,4-dioxohexane (IV), 6-phenyl-6-hydroxy-3-acetoxy-2,4-dioxo-hexane (VIII), and 6-phenyl-3-acetoxy-2, 4, 6-trioxohexane (X), were obtained.
  • Noriyoshi Inukai, Kohzi Nakano, Masuo Murakami
    1967 Volume 40 Issue 12 Pages 2913-2918
    Published: 1967
    Released: March 27, 2006
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    The S-ethylmercapto group was an useful protecting group for the thiol group of cysteine. This group was stable under the conditions of peptide synthesis and was simply split by thiophenol without any side reaction. Glutathione and oxytocin were synthesized using S-ethylmercapto-L-cysteine.
  • Tadashi Suehiro, Akihiro Nakagawa
    1967 Volume 40 Issue 12 Pages 2919-2924
    Published: 1967
    Released: March 27, 2006
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    5-Oxo-2-methyl-4, 4-dibenzyl-3-äthoxycarbonyl-4, 5-dihydroindol (I) ist ziemlich beständig gegen allgemeine Reduktionsmittel, wird aber reduziert mit Aluminium-Amalgam oder mit Natriumborhydrid. Bei der ersten Reduktion entsteht ein dimerer Alkohol. Bei der letzteren wird 5-Hydroxy-2-methyl-4, 4-dibenzyl-3-äthoxycarbonyl-4, 5, 6, 7-tetrahydroindol (III) gebildet. Die Hydroxy-Gruppe von III wird leicht bei der Behandlung mit Eisessig-Salzsäure oder -Schwefelsäure mit der Chlor- oder Acetyloxy-Gruppe unter Deäthoxycarbonylierung ausgetauscht. Dehydratisierung von III gelingt bei der Einwirkung von syrup. Phosphorsäure unter gleichzeitiger Deäthoxycarbonylierung and Umlagerung einer Benzyl-Gruppe in 2-Methyl-4, 5-dibenzyl-6, 7-dihydroindol (VII). VII lässt sich über Palladium-Kohle in 2-Methyl 4, 5-dibenzylindol (IX) dehydrieren, dessen Struktur synthetisch festgestellt wurde.
  • Tadashi Suehiro, Shigeru Sugimori
    1967 Volume 40 Issue 12 Pages 2925-2930
    Published: 1967
    Released: March 27, 2006
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    Direkte 4-Alkylierung von 5-Hydroxy-2-methyl-3-äthoxycarbonylindol (I) verläuft mit Cinnamylchlorid ausser mit Benzyl- und Allyl-chlorid, aber nicht mit Benzyloxymethylchlorid, Chloracetonitril, Bromessigester und Bromacetal. 4-Allylindol-Derivat IIb lässt sich auch durch Claisen-Umlagerung von 5-Allyloxyindol-Derivat IIIa herstellen. In Kombination der C-Benzylierung, C-Allylierung und der katalytischen Hydrierung mit der Claisen-Umlagerung kann man einige 5-Oxo-2-methyl-4, 4-dialkyl-3-äthoxycarbonyl-4, 5-dihydroindole IV darstellen. Beim Erhitzen von 5-Oxo-4, 4-diallyl-Verbindung IVb findet eine Umlagerung in 5-Hydroxy4, 6-diallyl-Derivat IIe statt, dessen Struktur synthetisch festgestellt wurde, während beim 5-Oxo-4,4-dibenzyl-Derivat IVa eine Benzyl-Gruppe unter Aromatisierung abgespaltet wird. Katalytische Hydrierung und Natriumborhydrid Reduktion von IV wurden mit einander vergleichend untersucht.
  • Zenichi Takayanagi, Hiroshi Kato, Masaki Ohta
    1967 Volume 40 Issue 12 Pages 2930-2936
    Published: 1967
    Released: March 27, 2006
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    The reduction of 4-thiazones and N-acetyl-4-thiazone-imines with sodium borohydride gave thiazolidin-4-ones and 4-acetylaminothiazolidines respectively. Attempts to isomerize 5-alkylidenethiazolidin-4-ones, prepared by the reduction of 5-acyl-4-thiazones, followed by dehydration, to 5-alkyl-4-thiazones were unsuccessful. The ethylation and acetylation of 2, 3, 5-triphenyl-4-thiazone gave the corresponding 4-ethoxy- and 4-acetoxy-thiazolium salts.
  • Shimao Sato, Hiroshi Kato, Masaki Ohta
    1967 Volume 40 Issue 12 Pages 2936-2938
    Published: 1967
    Released: March 27, 2006
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    An attempt to prepare 2-phenylazirine by treating acetophenone dimethylhydrazone methiodide with methylsulfinyl carbanion gave 2, 4-diphenylpyrrole instead of 2-phenylazirine. The reaction of 2-phenylazirine with the carbanions derived from acetophenone, ethyl benzoylacetate, and benzyl cyanide gave the corresponding pyrrole derivatives by ring enlargement.
  • Shimao Sato, Hiroshi Kato, Masaki Ohta
    1967 Volume 40 Issue 12 Pages 2938-2942
    Published: 1967
    Released: March 27, 2006
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    The reaction of 2-phenylazirine (I) with acid chlorides, anhydrides, an imidoyl chloride, and carboxylic acids were investigated. When I was treated with acid chlorides and anhydrides, the corresponding 2, 5-disubstituted oxazole derivatives were obtained. The reaction of I with phthalic and maleic anhydride, however, gave ring-cleavage products. The reaction of I and N-phenylbenzimidoyl chloride gave 1,2, 5-triphenylimidazole. On the other hand, I and benzoic and thiobenzoic acid gave N-benzoylphenacylamine and N-benzoyl-α-benzoylthio-β-aminostyrene respectively.
  • Sh\={o}suke S\={o}fuku, Ichiro Muramatsu, Akira Hagitani
    1967 Volume 40 Issue 12 Pages 2942-2945
    Published: 1967
    Released: March 27, 2006
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    A new method for the syntheses of phenyl and naphthyl formates has been devised. The formates were obtained in good yields from phenols and naphthols with acetic formic anhydride, which had been prepared from formic acid and ketene. The formyl ester of N-hydroxysuccinimide was also prepared by the same method.
  • Yoshihiro Hirotsu, Tetsuo Shiba, Takeo Kaneko
    1967 Volume 40 Issue 12 Pages 2945-2949
    Published: 1967
    Released: March 27, 2006
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    For the purpose of a total synthesis of bacitracin A, a synthetic method of the thiazoline peptide was investigated. A benzyloxycarbonylaminoalkylimino ethyl ether derived from glycine, L-alanine, L-valine, L-leucine or L-isoleucine was coupled with ethyl L-cysteinate hydrochloride to afford the corresponding thiazoline peptide, that is, a dehydrated form of cysteine peptide. While L-cystine was obtained from acid hydrolyzates of those thiazoline peptides, hydrolysis of them after treatment with alkali or ammonia gave DL-cystine. Furthermore, alkaline treatment caused a racemization of the amino acid residue adjacent to the thiazoline ring too.
  • Yoshihiro Hirotsu, Tetsuo Shiba, Takeo Kaneko
    1967 Volume 40 Issue 12 Pages 2950-2954
    Published: 1967
    Released: March 27, 2006
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    Synthesis of thiazoline peptide from cysteine peptide by dehydration with hydrochloric acid in non-aqueous solvent was investigated. By this method, ethyl 2-benzyloxycarbonylaminomethyl-R-Δ2-thiazoline-4-carboxylate and 2 - benzyloxycarbonylaminomethyl-R-Δ2-thiazoline-4-carbonyl-L-leucine ethyl ester were prepared and isolated in pure states. This synthetic method could give a promising route to a total synthesis of bacitracin A. However, the cysteine residue in the latter thiazoline peptide ester was found to be easily racemized under the basic condition.
  • Kaoru Tsuboyama, Sei Tsuboyama, Masaya Yanagita
    1967 Volume 40 Issue 12 Pages 2954-2957
    Published: 1967
    Released: March 27, 2006
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    Poly-(R)-2-ethylaziridine (I) was obtained by three different procedures: (A) the polymerization of (R)-2-ethylaziridine (II) by boron trifluoride-etherate, (B) the polymerization of the aziridine in the presence of ammonium chloride in liquid ammonia, and (C) the reaction of (R)-2-amino-l-bromobutane hydrobromide (III) with caustic alkali. The stereoregularity of the polymer I may be assumed to be fairly high as a result of comparing the specific rotations of the above polymers. In order to evaluate this assumption, the addition reaction of the aziridine and diethylamine was carried out as a model experiment under experimental conditions similar to those of the polymerization (A). On the basis of the data as analyzed by gas chromatography, it is concluded that the ring opening at the primary carbon takes place over 99.4%. This implies that the ring cleavage at the primary carbon in the polymerization occurs over 180 units successively. Considering the molecular weight of the polymer I (3500–5000, 50–70 monomer units), one can assume that the configuration of the polymers obtained here perfectly retains that of the monomer and that the polymer is “isotactic.”
  • Tetsuo Suami, Seiichiro Ogawa, Yasuo Nakashima, Hiroshi Sano
    1967 Volume 40 Issue 12 Pages 2958-2963
    Published: 1967
    Released: March 27, 2006
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    Bromination of epi-inosamine-2 in a mixture of acetyl bromide and acetic anhydride afforded 1, 5-dibromo-1, 5-dideoxy-rac-inosamine-6. From this compound, two hitherto unknown inosadiamines: myo-inosadiamine-2, 4 and muco-inosadiamine-2, 3, were obtained by displacement of the bromo groups by azide ions, followed by hydrogenation. The configurations of the new compounds obtained were established by the nuclear magnetic resonance spectra.
  • Kenji Sato
    1967 Volume 40 Issue 12 Pages 2963-2964
    Published: 1967
    Released: March 27, 2006
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  • Oyo Mitsunobu, Takashi Ohashi, Motokazu Kikuchi, Teruaki Mukaiyama
    1967 Volume 40 Issue 12 Pages 2964-2966
    Published: 1967
    Released: March 27, 2006
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