Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 39 , Issue 5
Showing 1-50 articles out of 61 articles from the selected issue
  • Yoshisada Ogino, Takeshi Kawakami, Toru Matsuoka
    1966 Volume 39 Issue 5 Pages 859-863
    Published: 1966
    Released: March 27, 2006
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    In order to investigate the surface properties of tungstic acid samples which had been compressed at pressures of 640–3840 kg./cm2, experimental studies concerning the catalytic activity for the vapor-phase hydration of propylene, the specific surface area, the pore structures, the surface acidities and the crystal structures were carried out. According to the experimental results, both the catalytic activity and the surface acidity became higher as the compressing pressure of the sample was increased, whereas the specific surface area remained practically constant. Further, a relation between the surface acidity and the crystal structure was deduced from X-ray diffraction studies. Namely, the crystal structure of the reduced sample approached the structure of H0.1WO3 from a WO3-like structure as the compressing pressure was increased. In other words, samples with higher compressing pressures had crystal structures of a higher proton content. In addition to the above results, the total pore volume, the mean pore radius, the apparent activation energy, and the frequency factor became smaller as the compressing pressure was increased. On the basis of these experimental results, it was deduced that the catalytic activities of the compressed samples are affected by intra-particle diffusion.
  • Kohzoh Sugiyama, Takehiko Takahashi
    1966 Volume 39 Issue 5 Pages 864-867
    Published: 1966
    Released: March 27, 2006
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    A phase diagram was drawn by using the results of a differential thermal analysis of the samples sealed in vicolglass and X-ray diffraction techniques undertaken in connection with the study of chlorine formation by the reaction of sodium chloride with sulfur dioxide and oxygen in the presence of iron compounds. In the two-component sodium sulfate - iron(III) sulfate system, the eutectic point was found at 562°C, the peritectic point, at 780°C, and the peritectoid point, at about 380°C. The former two values differ from those found by K. A. Bol’ shakov et al. (Zhur. Neorg. Khim., 8, 2577 (1963)). In the trigonal diagram, two eutectic points were found, one at 465°C with a composition of about 13.5 mol.% iron sulfate, 53.5 mol.% sodium chloride and 33.0 mol.% sodium sulfate, and the other at 454°C with 15.0 mol.% iron(III) sulfate on the line of sodium chloride - iron (III) sulfate. It was confirmed that the peritectic point corresponding to the Fe2(SO4)3+Na2SO4(1)=2NaFe(SO4)2 reaction shifted from 780°C on the line of sodium sulfate - iron(III) sulfate to 680°C on that of sodium chloride - iron(III) sulfate. From the diagram, the retarding tendency of the reaction rate of the final period of chlorine formation was attributed to diffusion control coming from the formation of solid phases.
  • Toshikazu Nagai, Kenichi Terauchi, Niichiro Tokura
    1966 Volume 39 Issue 5 Pages 868-874
    Published: 1966
    Released: March 27, 2006
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    The equilibrium constant, K, of the 1:1 charge-transfer complex formation of anthracene with sulfur dioxide has been estimated by spectrophotometric measurements to be 0.33 in carbon tetrachloride at 15°C. The values of ΔH (−4.8 kcal.mol−1) and ΔS° (−19 cal.deg−1mol−1) have been derived. The K value is nearly zero when estimated in the longer wavelength region, indicating that a contact charge-transfer complex is involved. A sort of contact charge-transfer complex of anthracene-SO2 is also observed in benzene. Irradiations by a high-pressure mercury lamp of anthracene with sulfur dioxide in various solvents have been carried out. In solvents such as n-hexane and carbon tetrachloride, which have no interaction with sulfur dioxide, anthracene gives sulfur-containing substances, such as anthracene-9-sulfonic acid (I) and dianthranyl-(9.9′)-sulfonic acid-(10) (II). On the contrary, in benzene or in carbon disulflde, no product such as the sulfonic acid, the dimer or the endoperoxide of anthracene is produced, indicating that the interaction of anthracene with sulfur dioxide is diminished by the solvent - sulfur dioxide interaction. A suggestion was made that the activated intermediate which induced the formation of I and II was of a singlet character.
  • Hazime Tanaka, Akira Matsumoto
    1966 Volume 39 Issue 5 Pages 874-879
    Published: 1966
    Released: March 27, 2006
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    Oxovanadium sulfate was fixed on silica and alumina gel bases as a model of the oxidation catalyst. On silica gel the ESR spectra showed an exchange narrowing without hyperfine lines as a result of the formation of small crystallites. In this case, axially-symmetrical g factors were obtained: g=1.969±0.001 and g||=1.915±0.005. When sulfuric salts of alkali metals were added to the system, the dispersion of VO2+ ions became homogeneous and a hyperfine structure was observed in the ESR spectra. On an alumina gel base the spectrum resembled that of the frozen aqueous solution of VOSO4 and showed the hyperfine structure, A=(7.0±0.2)×10−3cm−1 and A||=(1.85±0.05)×10−2cm−1. It may be considered that VO2+ ions are distributed homogeneously in the surfase layer of alumina. In the alumina gel and silica gel with alkali sulfate, the decrease in the V4+ ions with heat treatment was slower than in the silica gel system.
  • Teruaki Mukaiyama, Takanobu Kumamoto
    1966 Volume 39 Issue 5 Pages 879-882
    Published: 1966
    Released: March 27, 2006
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    The decomposition of benzil-triethyl phosphite adduct in the presence of copper powder or cupric sulfate has been studied. When benzil, triethyl phosphite and cupric sulfate were treated in boiling toluene. cis-dibenzoylstilbene and triethyl phosphate were obtained. When the reaction was carried out in the presence of active hydrogen compounds, such as alcohol, carboxylic acid and amine, the corresponding benzoin derivatives were obtained. Further, when the adduct was decomposed in the presence of phenyl isocyanate or dicyclohexylcarbodiimide, 3, 4, 5-triphenyl-4-oxazoline-2-one or 2-cyclohexylimino-3-cyclohexyl-4, 5-diphenyl-4-oxazoline was obtained, along with triethyl phosphate.
  • Hideo Otsuka, Ken Inouye, Makoto Kanayama, Fusako Shinozaki
    1966 Volume 39 Issue 5 Pages 882-888
    Published: 1966
    Released: March 27, 2006
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    The derivatives of lysyl-prolyl-valyl-glycyl-arginyl-arginine, lysyl-prolyl-valyl-glycyl-lysyl-arginyl-arginine and lysyl-prolyl-valyl-glycyl-lysyl-lysyl-arginyl-arginine, which correspond to the amino acid sequences in positions 11—14 plus 17—18, 11—14 plus 16—18, and 11—14 plus 11—18 of the corticotropin molecule respectively, have been obtained as intermediates for the synthesis of adrenocorticotropically active peptides.
  • Shuzo Aoki, Yoshiyuki Harita, Takayuki Otsu, Minoru Imoto
    1966 Volume 39 Issue 5 Pages 889-892
    Published: 1966
    Released: March 27, 2006
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    1,1-Dimethylcyclopropane and phenylcyclopropane gave the oligomer by aluminum bromide-catalyzed polymerization in n-hexane or in methylene chloride at 0°C. The polymerization reactivity of 1,1-dimethylcyclopropane was lower than that of styrene, and the content of cyclopropane units in their copolymers was decreased by a lowering of the temperature. The polymerization of 1,1-dimethylcyclopropane in the presence of polystyrene gave a graft polymer by chain transfer reaction. The polymerization of the cyclopropanes by a coordinated catalyst, C2H5AlCl2/TiCl3, in n-heptane at room temperature gave polymers with molecular weights of above 1200. The results are discussed in comparison with those of the polymerization of the corresponding vinyl monomers.
  • Akira Terakawa, Jun Nakanishi, Toru Hirayama
    1966 Volume 39 Issue 5 Pages 892-898
    Published: 1966
    Released: March 27, 2006
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    In a stainless steel autoclave, ethylene and hydrochloric acid or dried hydrogen chloride were irradiated with cobalt-60 gamma-rays. n-Butyl chloride and ethyl chloride were thus produced efficiently, unlike as when an ultraviolet light or catalyst was used. The products were quantitatively analyzed by gas chromatography. This reaction was supposed to be a vapor-phase radical chain reaction; the proposed reaction mechanism agreed well with our results. The selectivity of ethylene to the products was considered to be practically 100%. The G values of ethyl chloride, n-butyl chloride and the ethylene consumed, using the ratio of the total absorbed dose to ethylene, were calculated to be 16000, 10000 and 35000 respectively at 50°C and at a dose rate of 1.10×104r./hr. The ratios of the rate constants for ethyl chloride and n-butyl chloride were 366, 499 and 580 at 50, 40 and 15°C respectively, and the apparent activation energies for ethyl chloride and n-butyl chloride were calculated from the reaction rates to be 6.94 and 8.95 kcal./mol. respectively.
  • Masami Ichikuni
    1966 Volume 39 Issue 5 Pages 898-901
    Published: 1966
    Released: March 27, 2006
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    An estimation of the barium concentration in Tamagawa Hot Spring water was made on the basis of the partition of lead between spring waters and barite deposits precipitated from the waters. As the lead content of the waters and the chemical composition of the deposits are already known, the barium concentration can be computed by the use of the following relation:
    D=(\fracPbBa)S⁄(\fracPbBa)L
    where D is the partition coefficient of lead, and where S and L denote the solid and liquid phases respectively. A value of 2±1 mg./1. was obtained for the barium concentration in the water issuing from the vents. It was pointed out that the water is supersaturated with barium sulfate. This supersaturation may be due to the addition of a considerable amount of sulfates, probably formed by supergene processes, to the original thermal water. The genesis of hydrothermal barite deposits was also discussed.
  • Yukito Murakami, Katsuyuki Nakamura
    1966 Volume 39 Issue 5 Pages 901-909
    Published: 1966
    Released: March 27, 2006
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    The 3-phenyl- and 3-benzyl-2, 4-pentanedione complexes of trivalent aluminum, chromium, iron and cobalt were prepared, and their electronic absorption spectra measured in the 220—900 mμ range. The spectral data were interpreted in detail in terms of the π3→π4, the electron transfer (dε→π4) and the dd* transitions of the various components. In this series of complexes, an inter-ring π-interaction between a phenyl ring and a chelate ring is expected to remain to a limited extent in the metal complexes of 3-phenyl-2, 4-pentanedione, although the twist of both rings from the coplanarity is significant. For the aluminum complexes, π-electrons in the ligand part remain delocalized in a manner similar to that which holds in the corresponding enolate ion. On the other hand, each kind of π3→π4 transition in the transition metal complexes of the 2, 4-pentanedione derivatives was found to depend on the number of dε electrons of the central metal ion and to appear in this increasing order of energy: Cr<Fe<Co. In addition, the metal-ligand π-interaction has a major effect on the π3→π4 transition, and it seems to increase with respect to the ligands in the order: 2, 4-pentanedione, 3-phenyl-2, 4-pentanedione, and 3-benzyl-2, 4-pentanedione. The two major substituent (at the 3-position of 2, 4-pentanedione) effects which may affect the π3→π4 transitions were identified.
  • Masajiro Kawana, Sakae Emoto
    1966 Volume 39 Issue 5 Pages 910-916
    Published: 1966
    Released: March 27, 2006
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    Partial asymmetric syntheses were carried out in the reaction of Grignard reagents with crotonic and cinnamic esters of 1,2:5,6-di-O-cyclohexylidene-D-glucose, 1,2:5,6-di-O-isopropylidene-D-glucose, 1,2-O-isopropylidene-5-deoxy-D-xylose and (−)-menthol. The reaction of 3-O-crotonyl-1,2:5,6-di-O-cyclohexylidene-D-glucose (Ic) with phenylmagnesium bromide, followed by the hydrolysis of the resulting ester, gave (−)-3-phenylbutyric acid (III) in 33% optical and 12% synthetic yields, while in the presence of cuprous chloride as a catalyst, III was obtained in 74% and 58% yields respectively. The reaction of 3-O-crotonyl-1,2-O-isopropylidene-5-deoxy-D-xylose (Ie) with phenylmagnesium bromide gave (+)-acid (III) without cuprous chloride in 16% optical and 32% synthetic yields and (−)-acid (III) with cuprous chloride, in 58% and 61% yields respectively. The reaction of 3-O-cinnamoyl-1,2:5,6-di-O-cyclohexylidene-D-glucose (IVc) with benzylmagnesium chloride, followed by the saponification of the resulting ester, gave (−)-3,4-diphenylbutyric acid (VI) in 18% optical and 62% synthetic yields without cuprous chloride, and in 17% and 58% yields with cuprous chloride. In the formation of acid (VI), cuprous chloride seemed to have no effect on optical and synthetic yields nor on the change in the sign of optical rotation. The steric courses of these reaction are discussed.
  • Waichiro Tagaki, Kenji Ueyama, Isao Minamida, Yong He Kim, Yoshinori I ...
    1966 Volume 39 Issue 5 Pages 917-920
    Published: 1966
    Released: March 27, 2006
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    Some sulfides with benzylic hydrogen have been carboxylated by carbonating the respective carbanions generated with dimsylsodium in dimethyl sulfoxide. The resulting mercaptocarboxylic acids have then been found to have considerably-enhanced rates of decarboxylation reaction.
  • Nobuyuki Tanaka, Akifumi Yamada
    1966 Volume 39 Issue 5 Pages 920-925
    Published: 1966
    Released: March 27, 2006
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    The reduction of tris(ethylenediamine)chromium(III) ions at the dropping mercury electrode has been studied chronopotentiometrically in various supporting electrolyte solutions. The electrolysis at constant cathodic current in an acid solution gives a well-defined chronopotentiogram which corresponds to the one-electron reduction of chromium(III) to chromium (II). The anodic chronopotentiogram which is obtained by the current-reversal techniques is clearly separated from the cathodic one. Two cathodic steps are obtained in alkaline ethylenediamine solutions, and two anodic steps, at the current reversed. No chemical reaction involving hydrogen ions or ethylenediamine takes place prior to the electron transfer. The presence of very small amount of surface-active substances was found to improve the shape of chronopotentiograms. In the presence of EDTA, the one-electron cathodic chronopotentiogram splits into two steps.
  • Kozo Nagashima, Akira Kato
    1966 Volume 39 Issue 5 Pages 925-928
    Published: 1966
    Released: March 27, 2006
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    Chemical studies of thanlenite from Suishoyama pegmatite, Fukushima Prefecture, showed its composition to be very close to the ideal formula, Y2Si2O7, and to a selective distribution pattern of rare earths belonging to the thortveitite-type as defined by Goldschmidt and Thomassen. The X-ray powder studies disclosed a metamict state hitherto unknown in this species, and the original state could be recovered by thermal treatment. Optical and other properties: color, colorless to light gray; luster, resinous; optical properties, α=1.709±0.002, β=1.716±0.002, γ=1.723±0.002, (−)2V∼70°, ρ<v; specific gravity, 4.16, hardness; 6\frac12. Chemical analysis: SiO2, 30.68%; Al2O3, 0.10%; Fe2O3, 0.17%; ΣY2O3, 64.89%; UO2, 1.12%; ThO2, 0.20%; CaO,0.35%; MnO, 0.38%; MgO, 0.33%; Na2O, 0.02%; H2O(+), 1.56%; H2O(−), 0.11%; total, 99.91%.
  • Miki Goto, Masaki Konishi, Katsura Sugiura, Motoo Tsusue
    1966 Volume 39 Issue 5 Pages 929-932
    Published: 1966
    Released: March 27, 2006
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    The structure of N8-methylsepiapterin was previously postulated for a new pteridine from Bombyx mori lemon (This Bulletin, 38, 503 (1965)). This structure must, however, be modified on the basis of some new experiments. We will now present the 7, 8-dihydro-6-lactyllumazine structure for this compound.
  • Yoshimori Omote, Takeo Miyake, Seiya Ohmori, Noboru Sugiyama
    1966 Volume 39 Issue 5 Pages 932-935
    Published: 1966
    Released: March 27, 2006
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    From a study of the chemiluminescence spectra of acyl luminols (e.g., 3-acetylaminophthalhydrazide, 3-propanoylaminophthalhydrazide and 3-undecenoylaminophthalhydrazide) and of the corresponding fluorescence spectra of the reaction products, it is tentatively assumed that the emitting species of the chemiluminescence of acyl luminols in dimethylformamide-water (3:1 in vol.) is the corresponding 3-acylaminophthalate ion in the excited state.
  • Takehiro Abe
    1966 Volume 39 Issue 5 Pages 936-939
    Published: 1966
    Released: March 27, 2006
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    This paper has presented the expression for the frequency shift, including the solvent refractive index and the dielectric constant; the expression has been determined on the basis of a previous paper (This Bulletin, 38, 1314 (1965)). According to the present theory and E. G. McRae’s theory (J. Phys. Chem., 61, 562 (1957)), the excited state dipole moment of acetone has been estimated to be 0.86 and 1.84 D respectively, both being smaller than the ground state value. The results calculated by the present theory show that the excited state polarizability is 163.1×10−25 cm3 and that the solvation energies in the solvents of n-heptane, cyclohexane, carbon tetra-chloride, ethyl ether, and methyl acetate are less in the ground states than in the excited states.
  • Norichika Aoki, Tsunetaka Sasaki
    1966 Volume 39 Issue 5 Pages 939-944
    Published: 1966
    Released: March 27, 2006
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    The ion flotation of a cation by a cationic surfactant with the aid of an anionic chelating agent was studied for the system of Fe3+-ethylenediaminetetraacetic acid (EDTA)-octadecyldimethylammonium chloride (ODAC). The systems of Fe3+-EDTA and Fe3+-ODAC were also studied for purposes of comparison. The effects of the concentration of the above three components, the pH and the gas-flow time on the flotation efficiency were measured. The diagram of the flotation efficiency vs. the pH showed a W-shaped curve for the Fe3+-EDTA-ODAC system, which was explained by the formation of Fe3+-EDTA, Fe3+-ODAC and Fe3+-EDTA-ODAC complexes, each of which has a different optimum pH region of its formation. The flotation of a cation by an anionic surfactant was also studied using ferric, ferrous, silver and Malachite Green ions as cations and sodium dodecylsulfate (SDS) as an anionic surfactant. The flotation efficiency increased with the time of the gas flowing, except for the system of Fe3+-SDS. Such an increase was explained by the relatively insoluble nature of the corresponding SDS salts.
  • Teruo Matsuura, Kanji Omura
    1966 Volume 39 Issue 5 Pages 944-947
    Published: 1966
    Released: March 27, 2006
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    Various bromobenzene derivatives were irradiated in benzene with a low-pressure mercury lamp. The corresponding biphenyl derivatives were formed as the main products. A mechanism for the reaction has been discussed.
  • Shumpei Sakakibara, Masahiko Fujino
    1966 Volume 39 Issue 5 Pages 947-951
    Published: 1966
    Released: March 27, 2006
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    The synthesis of a hexapeptide amide, L-lysyl-L-phenylalanyl-L-isoleucylglycyl-L-leucyl-L-methionine amide, has been carried out as a demonstration of the t-amyloxycarbonyl method. This peptide is known to possess strong biological activity which is similar to that of eledoisin and bradykinin. During the synthesis, no complication occurred involving the t-amyloxycarbonyl group, and the final product had the expected activity. Therefore, it is considered that the t-amyloxycarbonyl method is useful for the synthesis of complicated peptides.
  • Takeshi Sawai, Yoshiharu Shinozaki, Gisuke Meshitsuka
    1966 Volume 39 Issue 5 Pages 951-955
    Published: 1966
    Released: March 27, 2006
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    The radiolysis of potassium iodide aqueous solutions has been studied in order to elucidate the contribution of the hydrated electrons to the radiolysis mechanisms. The deaerated and aerated solutions were irradiated by 60Co γ-rays under various conditions, and the yields of iodine, hydrogen peroxide, hydrogen and oxygen were determined. The pH dependences of the initial yields of iodine and hydrogen peroxide in the deaerated solutions are different from the results obtained in the aerated solutions. These results can be reasonably explained by assuming the hydrogen atoms and hydrated electrons to be the reducing species. From an examination of the results, the radiolysis mechanisms of the potassium iodide aqueous solutions have been discussed. The rate constant of the reaction of hydrated electrons for iodine has been calculated to be 5.9×1010 M−1 sec−1.
  • Takeshi Sawai
    1966 Volume 39 Issue 5 Pages 955-960
    Published: 1966
    Released: March 27, 2006
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    The determination of the yields of the two reducing species and the OH radical in the radiolysis of neutral aqueous solutions was undertaken, using deaerated 2-propanol aqueous solutions containing potassium nitrate or hydrogen peroxide as electron scavengers. Irradiation was carried out with 60Co γ-rays, and the hydrogen, nitrite ion, acetone, hydrogen peroxide and pinacol so produced were analyzed. The hydrogen yield decreases upon the addition of hydrogen peroxide or nitrate ions. The yield of hydrogen atoms is found to be 0.61±0.03 by subtracting the molecular yield of hydrogen from the total hydrogen yield in the solutions containing enough scavengers. The yield of nitrite ions increases with an increase in the concentration of nitrate ions, and decreases with an increase in the concentration of acetone and with a decrease in the pH value. The acetone yield increases sharply with an increase in the quantity of nitrate ions and reaches a plateau value in the concentration range of nitrate ions higher than 1×10−2M. In the presence of potassium nitrate of 1×10−2M, pinacol is not formed, and the yield of hydrogen peroxide is less than the molecular yield of hydrogen peroxide. On the basis of these results, radiolysis mechanisms are elucidated and the yields of the hydrated electron and the OH radical of a neutral solution are found to be 2.77±0.03 and 3.0 respectively. The relative rate constants, kH+NO3kH+(CH3)2CHOH and keaq+(CH3)2COkeaq+NO3, are found to be 0.18 and 0.78.
  • Michio Kobayashi, Asami Yamamoto
    1966 Volume 39 Issue 5 Pages 961-967
    Published: 1966
    Released: March 27, 2006
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    Mixed anhydrides of carboxylic acids and monoalkyl sulfites have been prepared, and their thermal decomposition has been studied. Some of these mixed anhydrides can be distilled without decomposition. Disproportionation to carboxylic anhydride and dialkyl sulfite is the main pathway of the thermal decomposition.
  • Michio Kobayashi
    1966 Volume 39 Issue 5 Pages 967-970
    Published: 1966
    Released: March 27, 2006
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    Sodium p-toluenesulfinate reacts with acetyl chloride to form acetic anhydride, p-toluenesulfinyl chloride, thiolsulfonate, and sodium p-toluenesulfonate. A reaction with benzoyl chloride gives benzoic anhydride in a good yield. A mixed anhydride of sulfinic acid and carboxylic acid is postulated as an intermediate, one which survives for a few hours at −60°C. The reaction mechanism is discussed.
  • Ikuko Akaza
    1966 Volume 39 Issue 5 Pages 971-980
    Published: 1966
    Released: March 27, 2006
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    The liquid-liquid extraction of alkaline earth metals was investigated with a TTA-MIBK solvent and a NH4OAc-AcOH-NH4OH aqueous solution in the presence of relatively large amounts of the metals. The extractability of the metal ions was in the decreasing order of magnesium, calcium, strontium and barium, while their distribution ratios were too close to one another for them to be separated from each other. Critical studies were made on several factors affecting the distribution of each metal, such as the amount of metal in the aqueous solution, the concentration of TTA in the organic solvent, and the pH of the solution. It was noticed that the concentration of TTA in MIBK played a principal role in this extraction and that the logD-log(TTA) relation was shown as a curve, not a straight line. The relation in other similar cases had usually been shown as a straight line, but the new results were obtained by compensating pH-change, the extent of which was variable with the concentration of TTA in the system. Among the metal ions, calcium and magnesium could be separated from each other by carrying out the extraction from their solution in the presence of EDTA. A further extention of this extraction to a reversed-phase partition chromatography will be undertaken and reported on in another paper.
  • Ikuko Akaza
    1966 Volume 39 Issue 5 Pages 980-989
    Published: 1966
    Released: March 27, 2006
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    The author’s preceding work, the liquid-liquid extraction of alkaline earth metals with TTA-MIBK, has now been extended to a reversed-phase partition chromatography in order to attain a good separation of the metal ions. The method was carried out with relatively large amounts of the metals through a column of Kel-F on which the organic phase of 1.5 M TTA-MIBK was supported. Elution was performed with 0.5 M buffer solutions, of various pH values, consisting of acetic acid, ammonium acetate and aqueous ammonia. The actual separation of each metal ion from the mixture of alkaline earth metals was achieved; the results are shown in several figures. The dependence of the distribution ratio on the pH of the solution and on the concentration of TTA in the stationary phase was examined from the elution curves; it might be considered that the same relation held as in the case of the liquid-liquid extraction system. Other experiments were then carried out in order to clarify the behavior of the TTA-chelates in the presence of a large amount of TTA; it was found that all of the TTA in the system participated in the effective extraction of the metal ion. The steps in the formation of the higher TTA-chelate in the column are depicted by the break-through curve of the chromatographic process.
  • Hazime Saitô, Teijiro Yonezawa, Shinichi Matsuoka, Kenichi Fukui
    1966 Volume 39 Issue 5 Pages 989-994
    Published: 1966
    Released: March 27, 2006
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    The intramolecular and intermolecular hydrogen bonds of the diol ethers are examined as model compounds of the diols by means of a study of their infrared and NMR spectra. The hydrogen bond shift and the intramolecular hydrogen bond shift are obtained. The value of the intramolecular hydrogen bond shift is discussed in terms of the electric field effect due to lone-pair electrons of the proton acceptor.
  • Shoichiro Yamada, Hiroaki Nishikawa, Emiko Yoshida
    1966 Volume 39 Issue 5 Pages 994-1002
    Published: 1966
    Released: March 27, 2006
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    Nickel(II) and copper(II) complexes of β-ketoamines derived from acetylacetone or benzoylacetone and aromatic amines have been newly synthesized and characterized. The aromatic amines included aniline, o-, m- and p-toluidine, o,o′-dimethylaniline, o,o′-diethylaniline, o-, m- and p-chloroaniline, and α- and β-naphthylamine. The configurations of these complexes in pyridine have been examined and compared with those in non-donor solvents. All these complexes are considered to be square-planar in non-donor solvents and in the solid state. The nickel-(II) complexes of the o,o′-disubstituted derivatives do not combine with pyridine molecules, whereas the corresponding copper(II) complexes readily combine with the pyridine molecule. The difference between nickel(II) and copper(II) ions is discussed in terms of the bonding nature of the metal ions. The β-ketoamines and salicylideneimines are also compared.
  • Yoko Kuroda, Akira Sasano, Masaji Kubo
    1966 Volume 39 Issue 5 Pages 1002-1006
    Published: 1966
    Released: March 27, 2006
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    The infrared absorption spectra of various urea complexes of copper(II) carboxylates were recorded and the assignments of observed frequencies have been carried out to various modes of vibration. On the basis of comparison of the observed spectra with those of related compounds, it is concluded that copper(II) carboxylate monoureas and hemiureas form dimer molecules in crystals as in copper(II) acetate monohydrate, that copper(II) formate bisurea dihydrate has a crystal structure bearing resemblance to that of copper(II) formate tetrahydrate, and that urea molecules in these urea complexes are involved in bonding by electrostatic forces or hydrogen bondings instead of being bonded to copper atoms by coordination bonds.
  • Toshio Nakagawa
    1966 Volume 39 Issue 5 Pages 1006-1008
    Published: 1966
    Released: March 27, 2006
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    The Gutowsky-Holm equation has been transformed into a formula which expresses the signal as a function of dimensionless parameters (a=2πτ|νA–νB|, r=1⁄2πT2A–νB| and pB) and a dimensionless variable (f=(ν–νA)/(νA–νB)). The shape function in this form is convenient for graphic representation and can be easily calculated for a desired combination of the parameters by using a suitable computer. The exchange rate can be determined by searching for a theoretical curve that agrees with the shape of the experimental signal.
  • Sukeya Kodama, Shin’ichi Fujita, Junsuke Takeishi, Osamu Toyama
    1966 Volume 39 Issue 5 Pages 1009-1014
    Published: 1966
    Released: March 27, 2006
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    The effect of a solvent cage on the photolysis of azoethane in n-heptane was investigated at 366 mμ, in the temperature range from −75 to 99°C. Among the gaseous products, nitrogen served as a measure of the azoethane decomposed. The other gaseous products were n-butane, ethane and ethylene; these three hydrocarbons accounted for ninety per cent of the decomposition at 0°C. The quantum yield of nitrogen was found to decrease with a lowering of the temperature. The value obtained at 0°C was 0.021. In the presence of a sufficient amount of styrene, which was used as a scavenger for ethyl radicals, the yields of the gaseous hydrocarbons were more or less reduced to constant values; from these the ratio of rate constants for the combination and disproportionation of the geminate ethyl radicals formed by the photolysis in a solvent cage was determined to be kcombkdisp=11.5exp(−371⁄RT). The fraction of ethyl radicals that reacted in these ways in the solvent cage, before escaping it, was dependent on the temperature; it decreased from 0.838 at −75°C to 0.467 at 99°C. In the absence of styrene, the reactions for ethyl radicals that escaped the original solvent cages were inferred to be hydrogen abstraction, addition, combination and disproportionation.
  • Yasuhiro Chigira, Mitsuo Masaki, Masaki Ohta
    1966 Volume 39 Issue 5 Pages 1014-1016
    Published: 1966
    Released: March 27, 2006
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    Deoxyaspergillic acid (I) and tetrahydrodeoxyaspergillic acid (II) were synthesized. 1-Chloro-3-methyl-2-pentanone was directly oximinated with hydroxylamine, and then the oxime was treated with L-leucine ethyl ester to yield N-(3-methyl-2-oximinopentyl)-L-leucine ethyl ester (III), which, on alkali-hydrolysis, followed by acid-hydrolysis, gave N-(3-methyl-2-oxopentyl)-l-leucine (IV). The treatment of the methyl ester of IV with ammonia gave I, and the hydrogenation of III on Raney nickel gave II.
  • Keishiro Shirahama, Kiyoshi Nakao, Hiroko Endo, Ryohei Matuura
    1966 Volume 39 Issue 5 Pages 1017-1019
    Published: 1966
    Released: March 27, 2006
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    The surface adsorptions of three sodium alkyl sulfates (C12, C14, C16) from dioxane-water mixtures have been measured by using 35S-labeled surfactants; it has been found to decrease with an increase in the dioxane concentration. This decrease has been explained in terms of the following factors; (1) the variation in the standard chemical potential of the surfactant in the bulk phase, or the free energy of transfer, (2) the surface tension of the solution, and (3) the dielectric constant of the solvent. In a solvent containing more dioxane than 40wt.%, it has been shown, both by experiment and by theory, that these alkyl sulfates lose their surface activities.
  • Shin’ichi Murayama
    1966 Volume 39 Issue 5 Pages 1019-1027
    Published: 1966
    Released: March 27, 2006
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    The papers of this series are kinetic studies of the reaction between phenol and formaldehyde in non-aqueous media; this reaction has, however, not been investigated as thoroughly as the reactions in aqueous media. During the course of the reaction, the reactants and products have been determined by gas chromatography. Within the range of low conversion, the overall reaction between phenol and methylal may be represented by:
    (Remark: Graphics omitted.)
    Moreover, the kinetic equation and the apparent activation energy have been estimated as follows :
    \fracd[methel alcohol]dt=−\fracd[phenol]dt=\frack[phenol]2[methylal]0[catalyst]1[methyl alcohol]3E\doteqdot18.6 kcl./mol.
    At the same time, methyl phenyl formal is detected as an intermediate in the reaction system. Judging from these experimental results, it seems that the acetal exchange reaction, and the substitution on aromatics proceed concurrently and consecutively in the complex system.
  • Shin’ichi Murayama
    1966 Volume 39 Issue 5 Pages 1027-1031
    Published: 1966
    Released: March 27, 2006
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    Methyl phenyl formal (MPF) is one of the most important intermediates in the acid-catalyzed reaction between phenol and methylal in non-aqueous media. On the acidic decomposition of MPF itself, phenol and methylal are mainly produced, along with a small amount of methyl alcohol at the first step; at the same time, there exists an equilibrium state between the reactants and the products. At the second step, the phenol produced is gradually consumed, and the reaction eventually yields methyl alcohol and such condensation products of phenol as methoxymethylphenol and dioxydiphenylmethane. Thus, the acetal exchange proceeds faster than the substitution on aromatics. On the other hand, the acidic decomposition of MPF is retarded remarkably by methyl alcohol, considerably by methylal, and fairly much by phenol. This behavior of MPF can be explained by its interaction with the catalyst and the opposing reactions with it. As a result, the reaction of MPF can better be understood.
  • Shin’ichi Murayama
    1966 Volume 39 Issue 5 Pages 1032-1035
    Published: 1966
    Released: March 27, 2006
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    In the previous papers of this series, the reaction between phenol and methylal in non-aqueous media has been investigated by means of the experimental characterization of the kinetic system; a plausible reaction scheme has thus been presented. The object of the present paper is to make a mathematical characterization of the kinetic system, a kinetic equation has been obtained by calculation based on the probable reaction scheme; it has been found to be in good agreement with the kinetic equation obtained experimentally.
  • Yoshio Sakai
    1966 Volume 39 Issue 5 Pages 1036-1039
    Published: 1966
    Released: March 27, 2006
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    The conversion of cellulose into soluble glucose polymers was shown to be composed of a set of irreversible reactions in series: A\xrightarrowk1B\xrightarrowk2C, where A is cellulose; B, a soluble glucose polymer, and C, the decomposition product, which does not give reducing sugar under further hydrolysis by dilute acid. The first-order rate constants, k1 (hr−1) and k2 (hr−1), were given in 0.32 to 3.3% sulfur dioxide solutions of sulfur trioxide:
    k1=2.64×1011C1.63exp[−16700⁄(RT)] (for 0–50°C),
    and k2=8.99×1015C1.63exp[−24500⁄(RT)] (for 25–50°C),
    From k1 and k2, the sulfur trioxide concentration, C, and temperature, T, the maximum yields of the soluble glucose polymer and the time required to attain a maximum yield were obtained. It was shown that the application of the technique to wood saccharification is possible.
  • Teisuke Obata, Masaaki Ueki, Teruaki Mukaiyama
    1966 Volume 39 Issue 5 Pages 1040-1042
    Published: 1966
    Released: March 27, 2006
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    This paper describes a successful method of preparing monoalkyl phosphates by the reaction of monobromocyanoacetamide with monobenzyl phosphite or inorganic phosphorous acid in the presence of alcohols. When equimolar amounts of monobromocyanoacetamide and either of the above-mentioned phosphorus compounds in alcohols were heated at about 100°C, the corresponding monoalkyl dihydrogen phosphates were obtained as anilinium salts in fairly good yields, together with cyanoacetamide and benzyl bromide or hydrogen bromide. The reaction can be interpreted in terms of a mechanism in which the initially-formed enol-phosphonium salts of cyanoacel amide are easily transformed to the second phosphonium salts by the action of the alcohols present from the salts, alkyl dihydrogen phosphates are produced.
  • Nobuyuki Tanaka, Tasuku Ito
    1966 Volume 39 Issue 5 Pages 1043-1048
    Published: 1966
    Released: March 27, 2006
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    The effect of nitrate ions on the polarographic waves of ethylenediaminetetraacetatoaquochromate(III) ions has been studied in acetate buffer solutions and acid potassium chloride solutions. Nitrate ions are chemically reduced in the vicinity of the mercury drop of the electrode by chromium(II)-EDTA complexes which are formed by the electroreduction of chromium (III)-EDTA complexes. The chromium (III)-EDTA complexes thus formed are reduced again at the DME and the intermediate products of nitrate ions are reduced further chemically with chromium (II)-EDTA complexes or electrochemically, resulting in the enhancement of the current. The nature of the limiting current is investigated and compared with that predicted from the theoretical treatment. The reaction between chromium(II)-EDTA and nitrate ions has also been investigated in acetate buffer solutions and its rate constant, 35 1. mol−1 sec−1 at nearly 0°C, μ=0.1, has been compared with 30 l. mol−1 sec−1, the value obtained from the polarographic catalytic current under almost the same condition.
  • Hiroshi Minato, Masayoshi Oku, Samuel Hung-Pui Chan
    1966 Volume 39 Issue 5 Pages 1049-1054
    Published: 1966
    Released: March 27, 2006
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    1,8-Di-p-tolyl-3,6-diphenyl-1,4,7-octaaztriene (DTDPO) was prepared by the potassium permanganate oxidation of 1-p-tolyl-3-phenyl-1-tetraazene (TPT), and the kinetics and the products of the decomposition of DTDPO were investigated. The experimental results can best be explained by assuming a mechanism in which DTDPO decomposes homolytically to yield a nitrogen molecule and two triazenyl radicals, which then combine to form 1,3,4,6-tetraaryl-1,5-hexaazdiene; the latter is very unstable and decomposes quickly to yield substituted azobenzenes and phenyl and p-tolyl radicals. The rather slow rate of decomposition of DTDPO was also discussed.
  • Hiroshi Minato, Takiko Fujisawa
    1966 Volume 39 Issue 5 Pages 1054-1058
    Published: 1966
    Released: March 27, 2006
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    The reaction between nitrosobenzene and hydrazine was studied. Aniline and nitrogen were found to be the products, but it was not certain whether or not phenyltriazene existed as an intermediate. Then the reaction between nitrosobenzene and phenylhydrazine was studied. The products were azoxybenzene, diphenylamine, benzene and nitrogen. The reaction between p-nitrosotoluene and phenylhydrazine yielded 4, 4′-azoxy toluene, 4-methyldiphenylamine, benzene and nitrogen. The mechanisms of these reactions were discussed on the basis of these findings.
  • Haruo Kuroda, Ryoichi Sudo
    1966 Volume 39 Issue 5 Pages 1059-1063
    Published: 1966
    Released: March 27, 2006
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    The crystalline powder of dianthraquinone changes its color from yellow to green when it is heated above 250°C. A heat-treated powder of a green color exhibits an ESR absorption, the line width of which is about 7 gauss, and the g-value, 2.0032. The intensity of the ESR absorption was studied as a function of the temperature of heat-treatment and the heating time. The activation energy for the formation of the paramagnetic species is estimated to be 74 kcal./mol. The X-ray diffraction patterns of heat-treated specimens indicate that a marked disorder is produced in the crystal structure by the heat treatment and that, finally, the dianthraquinone crystal becomes an amorphous solid. A close correlation can be found between the intensity of ESR absorption and the structural change. Polymerization occurs at higher temperatures and results in the formation of a dark green solid insoluble in organic solvents. It is suggested that the initial process of these thermal changes is associated with the thermochromism of dianthraquinone.
  • M. L. Mittal, S. S. Dube
    1966 Volume 39 Issue 5 Pages 1064-1065
    Published: 1966
    Released: March 27, 2006
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  • Takahiko Inazu
    1966 Volume 39 Issue 5 Pages 1065-1066
    Published: 1966
    Released: March 27, 2006
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  • M. A. Nabar
    1966 Volume 39 Issue 5 Pages 1067-1069
    Published: 1966
    Released: March 27, 2006
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  • S. Sriraman, V. Shanmugasundaram
    1966 Volume 39 Issue 5 Pages 1070-1071
    Published: 1966
    Released: March 27, 2006
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  • Toshiro Okamura, Iwao Satake, Ryohei Matuura
    1966 Volume 39 Issue 5 Pages 1071-1073
    Published: 1966
    Released: March 27, 2006
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  • Masato Yanase, Katsuhiro Ohno
    1966 Volume 39 Issue 5 Pages 1073-1075
    Published: 1966
    Released: March 27, 2006
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  • Toshio Sugita, Yuzo Inouye
    1966 Volume 39 Issue 5 Pages 1075-1076
    Published: 1966
    Released: March 27, 2006
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  • Yukito Murakami, Arthur E. Martell
    1966 Volume 39 Issue 5 Pages 1077-1079
    Published: 1966
    Released: March 27, 2006
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