Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 39 , Issue 1
Showing 1-44 articles out of 44 articles from the selected issue
  • Yoshinobu Takegami, Toru Ueno, Kiyoshi Kawajiri
    1966 Volume 39 Issue 1 Pages 1-7
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Some information on the mechanism of iron hydride formation in the reaction of iron (III) chloride with phenylmagnesium bromide under a hydrogen atmosphere has been presented. When the molar ratio (C6H5MgBr/FeCl3) is larger than 5, 3–4 (mol./mol. FeCl3) of hydrogen is absorbed during the synthesis of hydrides. The amounts of benzene, one of the by-products formed in the synthesis, have also been determined. The treatment of these hydrides with styrene under a nitrogen atmosphere has given ethylbenzene in amounts which correlate well with the amounts of hydrogen absorbed during the hydride synthesis. These observations can be taken as support for the formation of iron hydride. On the other hand, a mixture prepared by the reaction of iron(III) chloride with phenylmagnesium bromide under a nitrogen atmosphere evolved about 0.5 (mol./mol.FeCl3) of hydrogen on hydrolysis. When the hydride prepared under a hydrogen atmosphere was hydrolyzed with dideuterosulfuric acid, D2 as well as HD was evolved. These results seem to indicate that not only hydride sites but also metallic sites were formed during the iron hydride synthesis. On the basis of these observations, a possible mechanism for the formation of complex hydride containing iron and magnesium has been presented.
  • Ken-ichi Watanabe, Koji Sakai
    1966 Volume 39 Issue 1 Pages 8-14
    Published: 1966
    Released: March 27, 2006
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    Benzonitrile, benzyl cyanide, acetonitrile and 2-cyanopyridine give the corresponding amides by the hydration with nickel catalysts and water. The effect of pyridine and thiophene on the hydration has been investigated. In general, the yield of amides increases upon the addition of a suitable amount of pyridine. On the contrary, the reaction is distinctly suppressed by the addition of thiophene. This fact is in striking contrast to the effect on the hydrogenation of nitriles. The correlation of the catalytic functions in hydration and the hydrogenation of nitriles has been studied, and the hydration mechanism with nickel catalysts has been discussed.
  • Akihiro Kagemoto, Sachio Murakami, Ryoichi Fujishiro
    1966 Volume 39 Issue 1 Pages 15-19
    Published: 1966
    Released: March 27, 2006
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    The heats of dilution of atactic polystyrene (\barP=244)-various solvent systems have been measured by using a micro-twin-calorimeter at 25°C. Toluene, anisole, ethyl methyl ketone, dioxane and ethyl acetate were used as the solvents. For the analysis of the experimental data obtained by each dilution process, the simple Van Laar formula has been used, and the apparent enthalpy parameter between the polymer and the solvent has been derived. Since these interaction parameters seemed to depend on the concentration, we tried to analyze the experimental data with a modified Van Laar formula which contained interaction parameters depending on the concentration. The interaction parameters obtained by these analyses are considerably dependent on the concentration in good solvents, while those in poor solvents depend hardly at all on the concentration. This dependence of the interaction parameters on the concentration has been explained by using the dilute solution theory of polymer solutions proposed by Flory and Krigbaum (J. Chem. phys., 18, 1086 (1951)). The interaction parameters in the dilute region have been compared with those obtained by other methods, and the agreement between our values and those obtained by other methods has been found to be fairly good.
  • Katsutoshi Tamura, Kunio Nakatsuka, Ryoichi Fujishiro
    1966 Volume 39 Issue 1 Pages 20-25
    Published: 1966
    Released: March 27, 2006
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    A DTA apparatus for a polymer solution has been constructed. The heating rate was adjusted to approximately 0.50 or 0.42°C/min., a favorable rate for a polymer solution. From the DTA curves obtained by the use of this apparatus, the temperatures of the end points of the melting or dissolution have been determined; their plots give the solubility curves. The solubility of the isotactic polypropylene in decalin system increases monotonously with the increase in the temperature, except for the abnormality in the region from 30 to 50 wt.% in polymer content. In the case of the isotactic polypropylene-nitrobenzene system, on the other hand, the melting curve has a horizontal part in the region with a polymer content of less than 50 wt.%; above this point lies the phase separation curve, which touches the melting curve at the point with a polymer content of approximately 50 wt.%. The double peaks which appear in the DTA curve of the melting of pure isotactic polypropylene, may be due to the paracrystalline smectic modification of isotactic polypropylene, as has been suggested by Natta (Makromol. Chem., 35, 93 (1960)). The heat of fusion for isotactic polypropylene has been estimated to be approximately 1000 cal./unit mol. by measuring the area under the melting peak of the DTA curve and the equation for the melting point depression.
  • Toshinobu Higashimura, Tetsuro Miki, Seizo Okamura
    1966 Volume 39 Issue 1 Pages 25-30
    Published: 1966
    Released: March 27, 2006
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    In the solution polymerization of trioxane catalyzed by BF3·O(C2H5)2, the dependence of the molecular weight of the polymer formed on the polymerization conditions has been studied. In general, the molecular weight of the polymer formed increases in the course of polymerization, keeps a constant value over a certain range of conversion, and then again incerases remarkably. The molecular weight of the polymers formed decrease with an increase in the catalyst and water concentrations. This phenomenon can be explained qualitatively on the assumptions that the rate of the propagation reaction is smaller than that of the initiation reaction and that the chain breaking occurs through the reaction with water, which is consumed as the polymerization proceeds. This is equal to the assumption that the chain carrier is an oxonium ion in the cationic polymerization of trioxane.
  • Toshinobu Higashimura, Tetsuro Miki, Seizo Okamura
    1966 Volume 39 Issue 1 Pages 31-36
    Published: 1966
    Released: March 27, 2006
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    In the solution polymerization of trioxane catalyzed by BF3·O(C2H5)2, the dependence of the monomer concentration on the polymerization reaction has been studied. The kinetic order of the monomer concentration as determined from the course of polymerization is close to 2 (except in a non-polar solvent). The kinetic order of the initial monomer concentration is extraordinarily large in the polar solvent. On the other hand, the molecular weight of the polymers formed increases with an increase in the initial monomer concentration. In the polymerization of trioxane in a polar solvent such as nitrobenzene at a low monomer concentration, the molecular weight of the polymers does not increase in the course of polymerization, even at the initial stage of polymerization. The reason for this has been discussed in terms of the nature of the chain carrier.
  • Tetsuro Miki, Toshinobu Higashimura, Seizo Okamura
    1966 Volume 39 Issue 1 Pages 36-41
    Published: 1966
    Released: March 27, 2006
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    In the solution polymerization of trioxane catalyzed by BF3·O(C2H5)2 and boron fluoride, the dependence of the yield of CH2O produced in the induction period on the polymerization conditions has been studied at 30°C. In the case of the BF3·O(C2H5)2 catalyst, the formation of CH2O has been recognized in n-hexane just after the addition of the catalyst while no induction period of the polymerization was seen. In polar solvents, both the formation of CH2O and the polymerization were retarded as the water concentration increased. In these systems the concentration of the CH2O formed changed with time, and no equilibrium or stationary concentration was recognized. In the case of the boron fluoride catalyst, an increase in the water concentration remarkably increased the induction period, also. For either catalyst the induction period was not decreased by the addition of CH2O to the polymerization system in advance of the catalyst addition. Therefore, it has been deduced that, in the polymerization system catalyzed by BF3·O(C2H5)2, the polymerization and depolymerization reaction took place simultaneously and that the induction period was caused by water, which inhibits the formation of high polymers.
  • Tetsuro Miki, Toshinobu Higashimura, Seizo Okamura
    1966 Volume 39 Issue 1 Pages 41-46
    Published: 1966
    Released: March 27, 2006
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    The effect of the polarity of solvents in the solution polymerization of trioxane catalyzed by BF3·O(C2H5)2 has been studied. While the molecular weight of the resulting polymer is almost independent of the kind of solvent, the rate of polymerization in a polar solvent is large at a high initial monomer concentration. At a low monomer concentration, however, the rate of polymerization in a non-polar solvent is larger than that in a polar solvent. This fact can probably be explained by observing that, at the low monomer concentration, the initiation species produced from the catalyst is solvated by the solvent molecule rather than by trioxane because of the small basicity of trioxane. The activation energies of the over-all polymerization rate as determined in ethylene dichloride, nitroethane and nitrobenzene are all about 16 kcal./mol. The decrease in the molecular weight of the resulting polymers caused by raising the temperature is very small.
  • Akira Yokohata, Satoru Tsuda
    1966 Volume 39 Issue 1 Pages 46-52
    Published: 1966
    Released: March 27, 2006
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    In an atmosphere of helium or argon, the silent discharge reactions of aqueous solutions have been investigated from the point of view of radiation chemistry. A discharge tube with two coaxial glass tubes was used. In a dilute oxygen-free aqueous solution of sulfuric acid, hydrogen peroxide appeared as a result of discharge. Also, the oxidation of ferrous ions to ferric ions has been found. It has been confirmed, first, that neither the effect of metastable excited states of helium and argon nor that of luminescence is serious, and, second, that the reaction may well be interpreted by taking into consideration the actions of slow electrons generated in the gas phase on the liquid water. The yield of hydrogen atoms plus hydroxyl radicals has been estimated from the yields of hydrogen peroxide and ferric ions. The ratios of the yield of hydrogen peroxide to that of radicals show that the silent discharge reaction corresponds to the reaction by ionizing radiation of high LET, the value of which apparently equals 3eV./Å in helium and 8 eV./Å in argon. The G(Fe3+) value and the absorbed dose (E) estimated were, respectively, as follows: In helium: G(Fe3+)=4.6, E=3.8×106 r./hr.; in argon: G(Fe3+)=4.3, E=7.2×106 r./hr.
  • Akira Yokohata, Satoru Tsuda
    1966 Volume 39 Issue 1 Pages 53-55
    Published: 1966
    Released: March 27, 2006
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    In an atmosphere of helium or argon, the silent discharge reaction of an acidic aqueous solution of ceric sulfate has been investigated from the point of view of radiation chemistry. The results show the reduction of ceric ions to cerous ions. The situation is very similar to that in the case of radiation chemistry. From the known mechanism of the radiolysis of a ceric sulfate solution, the yield of “hydrogen atoms minus hydroxyl radicals” has been determined. Also, combining this yield with that of “hydrogen atoms plus hydroxyl radicals” previously obtained gave the respective yields of hydrogen atoms and hydroxyl radicals. Moreover, on the basis of the value of the dose rate previously determined, the G values of the hydrogen atom, the hydroxyl radical and the cerous ion were determined to be as follows: in helium: G(H)=1.1,G(OH)=1.6,G(Ce3+)=1.6; in argon: G(H)=0.6,G(OH)=0.7,G(Ce3+)=2.9. On the basis of these results, it may be concluded that the silent discharge reactions in an aqueous solution in inert gas can well be interpreted in terms of the radiolysis caused by the ionizing radiation of high LET.
  • Yoshio Matsumoto, Michiko Shirai
    1966 Volume 39 Issue 1 Pages 55-57
    Published: 1966
    Released: March 27, 2006
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    The observation of the orange-coloring reaction between potassium ferrocyanide and the chromium(III) ion on filter paper and its application in the paper chromatographical analysis of the chromium(III) ion has been reported on previously by the present authors. The color reaction has now been observed in an aqueous solution as well and studied in relation to the reaction temperature, the reaction time, the characteristic absorption, the species of chromium(III) salts, the chromium(III) ion concentration, the pH level, and the presence of an acetic acid buffer, by measuring the absorption spectra of the reaction solutions. The recommended conditions for getting a satisfactory color reaction and a suitable wavelength for the measurement of this color reaction have been presented.
  • Yoneichiro Muto, Hans B. Jonassen
    1966 Volume 39 Issue 1 Pages 58-64
    Published: 1966
    Released: March 27, 2006
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    Pyridine N-oxide copper(II) chloride, the structure of which has recently been elucidated by X-ray analysis [J. C. Morrow and H. L. Schäfer, private communication], has a subnormal magnetic moment (0.85 B.M. [J. V.Quagliano, J. Fujita, G. Franz, D. J. Phillips, J. A. Walmsley and S. Y. Tyree (J. Am. Chem. Soc., 83, 3770 (1961)]). It consists of a binuclear molecule [Cu(C5H5NO)Cl2]2 in which copper atoms are bridged in pairs by two oxygen atoms. In this work, copper(II) complexes with the empirical formulae of CuX2L, CuX2L2 and CuX2LY (X=Cl, Br;L=pyridine N-oxide, 3-picoline N-oxide, 4-picoline N-oxide, 4-chloropyridine N-oxide, 2,4-lutidine N-oxide, 2,4,6-collidine N-oxide, 4-nitroquinoline N-oxide; Y=N,N′-dimethylformamide, dimethylsulfoxide) have been prepared, and magnetic and spectral studies of these complexes have been made. The room-temperature magnetic susceptibilities of CuX2L complexes have been found to be correlated with the pKa (acid-dissociation constant) values of the attached N-oxides. The absorption band in the 735–900 mμ region (the so-called copper band) in the solid-state reflectance spectra of CuX2L complexes has been found to shift towards a lower frequency as the ligand field strength decreases, and a good parallelism between the frequencies and the magnetic moments has been observed. The effect of the attached ligand on the magnetic interaction has been discussed in terms of the electronic effect of the substituent on the pyridine ring. The infrared spectral data on the N–O stretching frequency indicate the absence of Cu–O–Cu linkage in the CuX2L2 complexes with normal magnetic moments.
  • Yonezo Morino, Takeshi Ukaji, Tetsuzo Ito
    1966 Volume 39 Issue 1 Pages 64-71
    Published: 1966
    Released: March 27, 2006
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    A high-temperature nozzle assembly for gas-electron diffraction has been designed and constructed. The molecular structure of gaseous arsenic at 485°C has then been investigated by the use of this nozzle. The regular tetrahedral structure of the molecule has been confirmed from the observed index of resolution; the interatomic distance has been determined to be rg(As−As)=2.435±0.004Å, while the mean amplitude has been determined for the first time (l(As−As)=0.085±0.006Å). The observed amplitude has led to the evaluation of the bond-stretching force constant, fr(As−As)=1.5±0.3 mdyn./Å.
  • Yonezo Morino, Takeshi Ukaji, Tetsuzo Ito
    1966 Volume 39 Issue 1 Pages 71-78
    Published: 1966
    Released: March 27, 2006
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    The precise molecular structures of arsenic triiodide and gallium triiodide in the vapor phase have been determined by the sector-microphotometer method of electron diffraction at the nozzle temperatures of 230°C and 255°C respectively. The results of gallium triiodide have confirmed the regular triangle structure of the molecule. The force constants of these molecules have been estimated from the observed mean amplitudes.
  • Keiichi Omori, Akitsugu Okuwaki, Takahiro Suzuki, Hiroshi Ito, Taijiro ...
    1966 Volume 39 Issue 1 Pages 78-83
    Published: 1966
    Released: March 27, 2006
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    On the reaction of an ammonium sulfite solution with a mixed solution of cupric sulfate and zinc sulfate, ten or more complex sulfite salts have been identified by chemical analysis and X-ray diffraction, and their formation regions have been shown with equilateral triangle coordinates. Their crystallographic properties have been examined through optical observation and X-ray diffraction. Usually some of them are formed simultaneously, but sometimes only one of them is formed, depending on the reaction conditions. The newly-found compounds are as follows:
    Cu2SO3·7(NH4)2SO3·9H2O Tetragonal
    Cu2SO3·ZnSO3·6(NH4)2SO3·10H2O Tetragonal
    Cu2SO3·2ZnSO3·5(NH4)2SO3·12H2O Monoclinic
    Cu2SO3·4ZnSO3·3(NH4)2SO3·12H2O Hexagonal
  • Satohiro Tanaka
    1966 Volume 39 Issue 1 Pages 84-88
    Published: 1966
    Released: March 27, 2006
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    A simple lattice theory of a non-electrolyte solution in which the equilibrium of chemical reaction is reached has been presented and compared with the data of the enolization of ethyl acetoacetate in various solvents and with those of the dimerization of nitrogen dioxide in chloroform. Predicted linear relationships has been obtained for the data of the enolization in non-polar solvents, but they could not be obtained for the reaction in ethyl alcohol or for the dimerization of nitrogen oxide in chloroform. The van’t Hoff-Dimroth relation has been derived by the present theory.
  • Kahei Sakaguchi, Kunihiko Nagase
    1966 Volume 39 Issue 1 Pages 88-91
    Published: 1966
    Released: March 27, 2006
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    The subsidence rate of a suspension of kaolin or precipitated calcium carbonate flocculated by polyacrylamide increases with an increase in the intrinsic viscosity of the polymer, and it shows a marked acceleration above an intrinsic viscosity of 5–6. However, in the case of the flocculation of the precipitated calcium carbonate flocculated by sodium polyacrylate, the subsidence rate depends linearly upon the intrinsic viscosity of the polymer. The results have been discussed in terms of Verwey and Overbeek’s theory. The real unperturbed dimension of polyacrylamide has been calculated from the equations proposed by Kurata, Stockmayer and Fixman. As a consequence, it has been suggested that the dimension of a polymer has a close relationship with its flocculation behavior.
  • Hitoshi Iwasaki, Yoshihiko Saito
    1966 Volume 39 Issue 1 Pages 92-100
    Published: 1966
    Released: March 27, 2006
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    Crystals of L-[Co l-pn3]Br3 (pn: propylenediamine) were prepared and their crystal structure was completely determined by means of X-rays. They are hexagonal, with the space group P63; a=11.08±0.03,c=8.59±0.02Å and Z=2. The structure is essentially ionic, consisting of complex ions and bromide anions. A complex ion has a three-fold axis of symmetry through the central cobalt atom. Five-membered Co-pn rings are puckered, and the C–C bonds in these rings are nearly parallel to the threefold axis. The methyl carbon bonds are equatorial with respect to the plane of the ring. The absolute configuration of the complex ion has been determined by using the absorption-edge technique. The Llll-type complex ion has been found to be laevorotatory with respect to the NaD lines. By the introduction of an asymmetric carbon atom into the ligands, the absolute configuration of a series of tris(bidentate)-complexes could be successfully correlated to the configurational series in organic compounds.
  • Shizunobu Hashimoto, Junzo Sunamoto
    1966 Volume 39 Issue 1 Pages 100-105
    Published: 1966
    Released: March 27, 2006
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    In the sodium monosulfide reduction of sodium m-nitrobenzene sulfonate, an induction period appears. The present investigation was undertaken in order to determine the causes of this induction period. The induction period is due not to the nitro compound, but to the reducing agent. The induction period is shortened by means of irradiation by ultraviolet light, the addition of potassium persulfate, ferric chloride, and α,α′-azobisisobutyronitrile, or under atmospheric conditions. On the other hand, the addition of phenol or alcohol lengthens the induction period. Further, on the basis of polarographic and spectroscopic studies of the induction period, it has been suggested that soduim disulfide is produced during this induction period. On the basis of these data, it seems reasonable to assume that, in the reduction of aromatic nitro compounds by sodium monosulfide, the reducing power of monosulfide is very small in itself, and that the nitro group is reduced by the disulfide produced by the radical oxidation of monosulfide. The formation of the sulfide ion radical and its dimerization appear to be responsible for the induction period of this reaction.
  • Shoichi Ikeda, Masakazu Maekawa, Toshizo Isemura
    1966 Volume 39 Issue 1 Pages 105-112
    Published: 1966
    Released: March 27, 2006
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    Poly-DL-alanine dodecylamide, prepared by the polymerization of N-carboxy-DL-alanine anhydride with dodecylamine initiation at different anhydride-to-initiator ratios, ([A]/[I]), is soluble in aqueous hydrochloric acid solutions to form micelles. Its micellar properties at pH 2.0 have been investigated by means of hydrodynamic methods. The material prepared at [A]/[I] 5 has a critical micelle concentration around 0.2—0.3 g. dl−1, which can be detected by Archibald sedimentation measurements. The micelle has been determined by the Archibald method to consist of about 13 monomer molecules. The molecules in the micelle are hydrogen bonded intermolecularly to form a structure similar to the β-conformation. Hydrogen bonding between peptide groups is more important for the micelle formation than hydrophobic bonds between dodecyl groups. The materials prepared at [A]/[I] 15 and 20 associate into large micelles, consisting of about 320 and 240 monomers respectively, as deduced from the sedimentation and viscosity measurements. The micelles exhibit even a flow birefringence. The structure of micelles seems to be a disordered one composed of randomly coiled monomer molecules; intermolecular hydrogen bonding and hydrophobic bonding are cooperative in its stabilization.
  • Michiro Hayashi, Yuji Shiro, Hiromu Murata
    1966 Volume 39 Issue 1 Pages 112-117
    Published: 1966
    Released: March 27, 2006
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    The infrared and Raman spectra of n-propyl mercaptan have been measured and vibrational assignments made with relation to the rotational isomerism. The normal vibration calculation has been carried out in a modified Urey-Bradley force field. In the gaseous and liquid states, TT and GT molecular forms have been confirmed to exist. An appreciable energy difference in the isomers has been found even in the liquid state. The TT form has a lower energy than the GT form. The CH2 hydrogen deformation frequencies of CH2CH2 groups in molecules similar to n-propyl mercatpan have been listed and discussed in relation to their molecular forms.
  • Michiro Hayashi, Yuji Shiro, Toshiyuki Oshima, Hiromu Murata
    1966 Volume 39 Issue 1 Pages 118-121
    Published: 1966
    Released: March 27, 2006
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    The infrared and Raman spectra of 1,2-dithiamethyl ethane have been measured in gaseous, liquid and solid states. Vibrational assignments have been made in relation to the rotational isomerism. The normal vibration calculation has been carried out in a modified Urey-Bradley force field. In the gaseous and liquid states, GTG′ and GGG molecular forms exist, while in the solid state the GTG′ form alone persists. The energy difference between GTG′ and GGG molecular forms has been found to be 1.1 kcal./mol. in the gaseous state and very small in the liquid state. The GTG′ form is more stable than the GGG form, in both the gaseous and liquid states.
  • Yukito Murakami, Michio Tanaka
    1966 Volume 39 Issue 1 Pages 122-127
    Published: 1966
    Released: March 27, 2006
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    The hydrolysis reaction of α-D-glucose 1-phosphate has been studied in the presence of several metal ions and metal chelates at 40.0 and 60.0°C, in the pH range of 1.69–2.71, and at an ionic strength of 0.10 M (KNO3). The reaction rate was followed by the colorimetric method using a combination of the amidol reagent and 8.3% molybdate solution. Among the metal ions employed in this work, dipositive ions, such as manganese(II), cobalt(II), nickel(II), copper(II), zinc(II) and uranyl ions, were observed to be nearly without effect on the rate of hydrolysis, while iron(III) and thorium(IV) ions demonstrated a negative catalytic effect. On the other hand, all the chelating agents employed tend to restore the reaction rate in reference to the corresponding metal-ion-effected reactions. With the 1:1 thorium(IV)-EDTA and the 1:1 iron(III)-EDTA chelate system, the rate was completely restored. Both iron(III)-kojate and thorium(IV)-Tiron chelate systems restored the reaction rate to a lesser extent. The roles of the chelating agents were discussed. The reaction mechanism in the presence of the catalyst species has been considered, and two possible mechanisms have been put forward for the present reactions.
  • Hitomi Suzuki, Kiyomi Nakamura, Ryozo Goto
    1966 Volume 39 Issue 1 Pages 128-131
    Published: 1966
    Released: March 27, 2006
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    The following polyalkylbenzenes bearing bulky groups have been subjected to direct iodination using iodine and periodic acid, and the corresponding mono-iodinated products have been obtained in fairly high yields: 4-t-butyl-1, 2-dimethylbenzene, 5-t-butyl-1, 3-dimethylbenzene, 5-t-butyl-1, 2, 3-trimethylbenzene, 1, 2, 4, 5-tetraisopropylbenzene and p-di-t-butylbenzene. The polyiodination of polymethylbenzenes has also proceeded smoothly, giving polyiodo compounds in high yields. A comparison of various direct methods has proved the above reagent to be the best iodinating agent for a variety of polyalkylbenzenes.
  • Fuminori Akiyama, Niichiro Tokura
    1966 Volume 39 Issue 1 Pages 131-137
    Published: 1966
    Released: March 27, 2006
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    The propionylation and p-methoxybenzoylation of l-menthol in various solvents have been studied. In chloroform, benzene, ethyl methyl ketone and carbon tetrachloride, the reaction follows the second-order rate law. However, in acetonitrile or in liquid sulfur dioxide, the rate follows the second-order rate law only at the initial stage of the reaction; thereafter it gradually deviates from the second-order type to the first-order one. Moreover, the first-order rate equations both in acetonitrile and liquid sulfur dioxide are dependent on the initial concentration of the alcohol; the over-all rates being expressed as:
    Rate=k1°(AcCl)(ROH)0+k2(AcCl)(ROH)
    where(ROH)0, (ROH), (AcCl), k1° and k2 are the concentrations of the alcohol at time zero and t, that of the acyl chloride at time t, the first-order rate constant and the second-order rate constant respectively.
  • Masaaki Ohara, Chau-Yang Chen, Takao Kwan
    1966 Volume 39 Issue 1 Pages 137-140
    Published: 1966
    Released: March 27, 2006
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    The selective adsorption of D- or L-mandelic acid on starch from an aqueous solution of racemate has been quantitatively investigated. L-Mandelic acid has been judged from the distinct negative value of the optical rotation in the solution to be adsorbed preferentially over the D-isomer. The separation factor for the adsorption of the two enantiomers was 1.06±0.02 at 0°C. From the saturation value estimated by the Langmuir equation for adsorption, the ratio of the glucose residue to the DL-mandelic acid adsorbed has been calculated as 5, indicating that not all the glucose residues in the starch constitute adsorption sites for mandelic acid.
  • Jiro Tsuji, Shuntaro Hosaka, Jitsuo Kiji, Tosaku Susuki
    1966 Volume 39 Issue 1 Pages 141-145
    Published: 1966
    Released: March 27, 2006
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    The 1,5-cyclooctadiene - palladium chloride complex and carbon monoxide react in ethanol to form ethyl 4-cyclooctenecarboxylate. The carbonylation of 1,5-cyclooctadiene catalyzed by palladium chloride has given ethyl 4-cyclooctenecarboxylate and cyclooctanedicarboxylate. It has been found that the monoester can be obtained selectively under certain conditions; the further carbonylation of the monoester gives the diester. Under the same reaction conditions, 1,3-cyclooctadiene gives ethyl 2-cyclooctenecarboxylate in a low yield. Metallic palladium has been found to be the true catalyst and the presence of hydrogen chloride has been found to be essential for the catalysis. It has also been found that the 1, 5-cyclooctadiene - palladium chloride complex can be formed from 1,5-cyclooctadiene, metallic palladium and hydrogen chloride by heating them in an autoclave under nitrogen. It seems likely that the catalytic carbonylation of 1,5-cyclooctadiene proceeds through the formation of the 1,5-cyclooctadiene - palladium chloride complex.
  • Jiro Tsuji, Tatsuo Nogi
    1966 Volume 39 Issue 1 Pages 146-149
    Published: 1966
    Released: March 27, 2006
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    The carbonylation of 1, 5, 9-cyclododecatriene has been carried out in ethanol in the presence of palladium chloride; mono- and diesters have thus been obtained without ring contraction. It has been observed, by means of a study of the NMR and infrared spectra, that the first attack of carbon monoxide occurred at the trans double bond, giving ethyl cyclododecadienecarboxylate. The second attack of carbon monoxide occurred randomly, giving an isomeric mixture of ethyl cyclododecenedicarboxylate. No triester was obtained even under prolonged carbonylation. The true catalyst has been found to be metallic palladium, and the presence of hydrogen chloride has been found to be essential for the catalysis. The oxidation of ethyl cyclododecadienecarboxylate, followed by esterification, has given ethyl succinate and 1, 3, 6-hexanetricarboxylate. This result indicates that the double bonds of ethyl cyclododecadienecarboxylate remain at the original positions.
  • Akio Hashizume, Nobuhide Wasada, Toshikazu Tsuchiya
    1966 Volume 39 Issue 1 Pages 150-155
    Published: 1966
    Released: March 27, 2006
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    Phosphorus pentoxide has been investigated with a mass spectrometer over the temperature range from 60°C to 650°C. A Knudsen cell has been installed in the source of the mass spectrometer. Two samples were used in the experiment. One was commercially-available phosphorus pentoxide, while the other had been purified from the commercial phosphorus pentoxide by Finch’s method. The ionization efficiency curves near the appearance potential of P4O9+ and P4O10+, the fractional yield of each ion versus the ionizing voltage have been investigated and interpreted as evidence for the presence of the P4O9 molecule. Three curves representing the intensity of the mass 284 (P4O10+) peak as a function of the temperature have been obtained. Two of them, which set on at about 250°C and 450°C respectively, are related to the known vapor pressure curves of phosphorus pentoxide. The curve with the lowest onset temperature, about 100°C, may be interpreted as a vapor pressure of a new low temperature phase of phosphorus pentoxide.
  • Shin Sato, Rei Yugeta, Kyoji Shinsaka, Terumi Terao
    1966 Volume 39 Issue 1 Pages 156-160
    Published: 1966
    Released: March 27, 2006
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    Nitrous oxide has been used as an electron scavenger in the radiolysis of hydrocarbons: cyclohexane, cyclohexene, benzene, and their mixtures. Considering that the energy for the formation of an ion pair is about 25 eV. in hydrocarbons, 0.4mol.1−1 of nitrous oxide is not enough to capture all the electrons ejected from irradiated hydrocarbons. In the case of cyclohexane, 70% of the ejected electrons seem to be captured by 0.4mol.1−1 of nitrous oxide. In the case of benzene, G(N2) is about a half of that for cyclohexane. This has been explained tentatively in terms of the ability of benzene to capture electrons. The G(N2)’s in the cases of cyclohexene and benzene have not shown any noticeable dependence on the concentration of nitrous oxide. This shows that hydrogen does not result from the neutralization in these systems. In order to clarify them, the primary processes in the radiolysis of cyclohexane have been further considered using the data previously obtained.
  • Akira Fujino, Kousuke Kusuda, Takeo Sakan
    1966 Volume 39 Issue 1 Pages 160-164
    Published: 1966
    Released: March 27, 2006
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    Perchloro-(3,4-dimethylenecyclobutene) has been converted to 1, 3′, 3′, 4′, 4′-pentachloro-2-methoxy-3,4-dimethylenecyclobutene; in some solutions exposed to the air, this then gradually decomposed to perchloro-(dimethylene-1, 2-cyclobutanedione). The further spontaneous degradation of the last compound in an aqueous ethanol solution has also been investigated in order to elucidate the structures of an unstable intermediate (an adduct of ethanol to the carbonyl) and the end product (the hemi-ketal lactone ester). The physical and chemical properties of these compounds have been given and discussed. A possible bicyclic intermediate caused by the interaction between the hydroxyl group and the diagonally-positioned dichloromethylene group in above unstable ethanol adduct has been suggested in the process from the latter compound to the end product.
  • Tsunenobu Shigematsu, Masayuki Tabushi, Masakazu Matsui, Takaharu Honj ...
    1966 Volume 39 Issue 1 Pages 165-169
    Published: 1966
    Released: March 27, 2006
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    The Synergistic effect of many kinds of oxygen- and nitrogen-containing solvents on the extraction of europium ions with benzoyltrifluoroacetone in n hexane has been studied. The addition of alcohols, esters, ketones amines and heterocyclic compounds enhances the extraction, and in general, the solvents with longer carbon chain, especially alcohols and amines, have the larger synergistic effects. At a constant benzoyltrifluoroacetone concentration, the logarithm of the distribution coefficients is linear with pH. The slope of the log D vs. pH plot is about 1.5 in the extraction with 0.05 M benzoyltrifluoroacetone in n hexane, but it is 2 in the presence of 0.04M oxygencontaining compound and 3 in the presence of 0.04 M nitrogen-containing compound. It may be considered that europium benzoyltrifluoroacetonate forms some adducts with these oxygen-or nitrogen-containing lewis bases, and that the coordination of nitrogen-containing lewis bases to the chelates is stronger than that of oxygen containing ones.Since the solvent extraction of neodymium and lutetium ions with β-diketones is performed as well as that of europium ions, it seems to be a favorable procedure for the extraction of rare earth ions with β-diketones to utilize the adduct formation between β-diketonates and active oxygen- or nitrogen -containing Lewis bases.
  • Tetsuo Suami, Frieder W. Lichtenthaler, Seiichiro Ogawa
    1966 Volume 39 Issue 1 Pages 170-178
    Published: 1966
    Released: March 27, 2006
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    muco-Inosamine-1, scyllo-inosamine, muco-inosadiamine-1,5 and myo-inosadiamine-1,2 have been synthesized from myo-inositol. Their structures have also been established by a study of the NMR spectra of their acetyl derivatives. When 1, 4, 5, 6-tetra-O-acetyl-3-O-mesyl-myo-inositol is treated with sodium azide in boiling aqueous 2-methoxyethanol, an azido derivative is obtained. The azido compound is hydrogenated in the presence of a catalyst and subsequently acetylated to give muco-inosamine-1. The stereochemical course of the reaction has been proposed to be an anchimeric reaction. When the analogous reaction is carried out with 2,3-di-O-mesyl-myo-inositol tetraacetate, myo-inosadiamine-1,2 or muco-inosadiamine-1,5 is obtained as the main product, depending on the solvent applied.
  • Fumikatsu Tokiwa
    1966 Volume 39 Issue 1 Pages 179-185
    Published: 1966
    Released: March 27, 2006
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    The way in which a cationic polysoap, prepared by quaternizing the nitrogen of poly-2-vinylpyridine with n-dodecyl bromide, interacts with additives, such as a cationic monosoap (n-dodecyl-α-picolinium bromide), a non-ionic surfactant (polyoxyethylene dodecyl ether) and potassium bromide, has been studied in aqueous solutions in terms of the viscosity and solubilizing power for oil-soluble dyes of the mixed solutions of the polysoap and the additives. An experiment on the effects of these additives on the behavior of a polyelectrolyte (poly-2-vinyl-N-ethylpyridinium bromide), prepared from the same parent polymer as the polysoap, has also been included for the purpose of comparison. The hydrophobic hydrocarbon chains in the polysoap and additive molecules play an important role in the interaction of the polysoap with the additives. Co-micellization or mixed micellization occurs between the polysoap and the monosoap or the non-ionic surfactant in aqueous solutions.
  • Mamoru Fujinaga, Yoshio Matsushima
    1966 Volume 39 Issue 1 Pages 185-190
    Published: 1966
    Released: March 27, 2006
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    The efficiency of hydrazine as a mild N-deacetylating reagent has been studied in the reaction of hydrazine with four N-acetylaminosugars. This reagent has been shown to be of great use in the N-deacetylation of methyl N-acetyl-β-D-glucosaminide and methyl N-acetyl-4,6-O-ethylidene-α-D-glucosaminide. It may be noted that the 3-O-substitution of the sugars makes the deacetylation reaction reluctant. The synthesis of methyl N-acetyl-4,6-O-ethylidene-α-D-glucosaminide and the isolation of crystalline methyl β-D-glucosaminide and methyl 4,6-O-ethylidene-α-D-glucosaminide in the free-base form have been described.
  • Yonezo Morino, Takeshi Ukaji, Tetsuzo Ito
    1966 Volume 39 Issue 1 Pages 191
    Published: 1966
    Released: March 27, 2006
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  • Hajime Ishii, Hisahiko Einaga
    1966 Volume 39 Issue 1 Pages 193
    Published: 1966
    Released: March 27, 2006
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  • Katsuya Uesugi, Yukiteru Katsube
    1966 Volume 39 Issue 1 Pages 194
    Published: 1966
    Released: March 27, 2006
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  • Yusuf Ahmad, Shamim Ahmad Shamsi
    1966 Volume 39 Issue 1 Pages 195
    Published: 1966
    Released: March 27, 2006
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  • Masaji Miura, Akinori Hasegawa
    1966 Volume 39 Issue 1 Pages 196
    Published: 1966
    Released: March 27, 2006
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  • Kashiro Kuroda, Motoko Goto
    1966 Volume 39 Issue 1 Pages 197
    Published: 1966
    Released: March 27, 2006
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  • Shinji Murai, Shigeru Tsutsumi
    1966 Volume 39 Issue 1 Pages 198
    Published: 1966
    Released: March 27, 2006
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  • Hisaharu Hayashi, Koichi Itoh, Saburo Nagakura
    1966 Volume 39 Issue 1 Pages 199
    Published: 1966
    Released: March 27, 2006
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  • Tadaaki Nishihama, Takeyoshi Takahashi
    1966 Volume 39 Issue 1 Pages 200
    Published: 1966
    Released: March 27, 2006
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