Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 40 , Issue 8
Showing 1-50 articles out of 61 articles from the selected issue
  • Koji Nobutoki, Hiroshi Sumitomo
    1967 Volume 40 Issue 8 Pages 1741-1745
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    ε-Caprolactone was polymerized by using living polystyrene prepared by means of an anionic polymerization technique. A gross polymer was elution-fractionated into four fractions which were methanol-soluble low-molecular-weight polyester, high-molecular-weight polyester, a small amount of polystyrene and polystyrene-polyester block copolymer. Both yields and molecular weights of block copolymers were observed to be higher in benzene than in tetrahydrofuran. Formation of block copolymers was concluded from the results of an elementary- and infrared analyses and turbidometry. Polymerization mechanism of ε-caprolactone is discussed.
  • Wahid U. Malik, Hasan Arif, Fasih A. Siddiqi
    1967 Volume 40 Issue 8 Pages 1746-1753
    Published: 1967
    Released: March 27, 2006
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    The permeability and membrane potential of various electrolytes, through parchment supported silver and cadmium ferro- and ferricyanide membranes was investigated. The order of permeability was found to be:
    Cl>NO3>SO4−2>FeCy6−3>FeCy6−4
    while membrane potential was of the reverese order. The magnitude of permeability and potential values, decreases or increases respectively, with potassium ferro- or ferricyanide treated membranes. The relation y=ax1⁄n where x and y represents permeability and potential respectively, and a and n are constants, proposed earlier has been found to be valid for these membranes also. The energy of activation for the diffusion process for various electrolytes was found to lie between 4 to 10 kcal/mol. The potential values determined at varying concentrations of electrolytes, showed that the values increase with dilution. The electronegative character of the membranes, have got a profound influence on the movement of the anions. When the concentration of the electrolyte within the pores are higher, the repulsion of the fixed charges are reduced by screening, that is, at higher concentrations the selectivity of the membrane is decreased to an appreciable extent, resulting thereby in a marked decrease in membrane potential and increase in the permeability values.
  • D. N. Chaturvedi, O. P. Bansal
    1967 Volume 40 Issue 8 Pages 1753-1755
    Published: 1967
    Released: March 27, 2006
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    The copper ferrocyanide and zinc ferrocyanide sols have been prepared, and their precipitation values have been studied by using KCl, BaCl2 and AlCl3 and by employing the spectrophotometric method in the light of the equation:
    C=a+\fracm·1⁄tn+1⁄t
    It has been found that the values of a and m remain the same at all stages of coagulation, while the value of n depends to a great extent on the coagulation stage.
  • Chandra Prakash, S. N. Srivastava
    1967 Volume 40 Issue 8 Pages 1756-1765
    Published: 1967
    Released: March 27, 2006
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    Role of pepsin as emulsifier in the stability of Nujol-in-water system has been studied. The flocculation studies were carried out haemocytometrically at different pH values, different amounts of electrolytes and different amounts of emulsifier itself. The zeta potential measurements were carried out at different pH values and varying amounts of electrolytes. In the light of the D. V. O. theory the interaction energy profiles have been drawn by summing up the repulsion and attraction energies. The high energy barriers obtained obviate the possibility of the occurrence of the flocculation in the primary minima. It appears, therefore, that the reversible flocculation occurs in the secondary minima which are about 2 to 4 kT deep. Therefore, assuming a singlet-doublet equilibrium degrees of aggregations have been calculated. In order to explain the observed values of degrees of aggregations, A (van der Waals constant) should be ≈5.97×10−13 erg. This value has been obtained by an indirect approach to fit the aggregation data. In case of Al(III) and Th(IV), however, charge reversal takes place which has been explained by a model picture. Charge densities and binding parameters have also been calculated.
  • Shin-ichi Ohno
    1967 Volume 40 Issue 8 Pages 1765-1769
    Published: 1967
    Released: March 27, 2006
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    The photochemistry of hexacyanoferrate(II) ions in aqueous solutions was studied at 3660 Å in the presence and in the absence of nitrous oxide as an electron scavenger. Only a photo-aquation reaction yielding aquopentacyanoferrate(II) and cyanide ions was observed to occur as the primary process. The formation of aquopentacyanoferrate(II) ions, determined spectrophotometrically after a reaction with sodium azide, was studied as a function of the irradiation time over a wide pH range (0.5 to 13). In neutral or alkaline solutions the amount of aquopentacyanoferrate(II) ions measured was small, because of an efficient thermal back reaction. The initial quantum yield depended on the pH; for example, the yield 0.52 at pH 0.65 and 0.89 at pH 4.0 for 0.01 M solutions at 25 °C. The yield decreased with an increase in the hexacyanoferrate(II) concentration.
  • Shin-ichi Ohno
    1967 Volume 40 Issue 8 Pages 1770-1775
    Published: 1967
    Released: March 27, 2006
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    The effects of 2537 Å radiation upon solutions of hexacyanoferrate(II) were investigated at 25°C, using specific scavengers for hydrated electrons (N2O, H3O + , and NO3) and for hydrogen atoms (CH3OH and C2H5OH). In the presence of N2O or NO3, a photo-oxidation reaction giving hexacyanoferrate(III) was found to take place, the primary process being:
    [Fe(CN)6]4−\xrightarrowhν[Fe(CN)6]3−+eaq
    The quantum yield of this photochemical process was determined to be 0.35 at 25°C. The eaq thus formed reacted with N2O, NO3, and H3O+ , just like the hydrated electron produced in water irradiated with fast electrons or γ-rays.
  • Shin-ichi Ohno
    1967 Volume 40 Issue 8 Pages 1776-1779
    Published: 1967
    Released: March 27, 2006
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    The photochemistry of the hexacyanoferrate(II) ion was investigated at 2537Å in the presence of acetone and of N2O or NO3. Acetone was found to act as a scavenger for the photo-chemically-produced electron, thus giving an acetone radical which can reduce the hexacyanoferrate(III) ion to the -(II) ion. The relative reaction rates of the electron, k(eaq+acetone)/ k(eaq+N2O) and k(eaq+ acetone)/k(eaq+NO3), were found to be 1.5 and 0.45 respectively. These rate ratios were found to vary with the ionic strength value in a way which indicates that eeq has a unit negative charge and survives long enough for the establishment of its ionic atmosphere.
  • Shin-ichi Ohno
    1967 Volume 40 Issue 8 Pages 1779-1783
    Published: 1967
    Released: March 27, 2006
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    The effects of environmental changes, such as temperature changes, the addition of salts, and the use of D2O as a solvent, upon the absorption spectrum of the hexacyanoferrate(II) ion, as well as upon the photochemical yield of hydrated electrons, have been investigated. The results observed have then been tentatively interpreted in terms of a proposed mechanism: (1) the absorption of light quanta results in an “internal” metal-(d)→ CN-(π*) excited state; (2) the rate of the detachment of an electron from this excited state to the solvent is dependent on the size of the cavity occupied by the complex ion surrounded by the hydration layers of the water, and (3) environmental changes affect the size of the cavity, thus influencing the magnitude of the quantum yields of eap.
  • Sachio Murakami, Ryoichi Fujishiro
    1967 Volume 40 Issue 8 Pages 1784-1789
    Published: 1967
    Released: March 27, 2006
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    A calorimeter for measuring the heat of mixing was constructed. Using the calorimeter, the heats of mixing were measured at 25.0±0.01°C for binary mixtures of benzyl alcohol with ethyl benzene or cyclohexane and ethyl benzene with cyclohexane, and at 35.0±0.01°C for binary mixtures of m-cresol with m-xylene or cyclohexane and m-xylene with cyclohexane. By plotting the values of the heats of mixing, ΔHx1M against the mole fraction of component 1, x1 and by extrapolating the curve to an infinite dilution (x1→0) for each system, the heats of mixing at an infinite dilution (\undersetx1→0limΔHx1M) were obtained graphically. By using the values of \undersetx1→0limΔHx1M obtained for these systems and by applying an enthalpy cycle, the OH–π type intermolecular hydrogen bond energies were estimated to be ΔH=−6.2 kJ for the benzyl alcohol-ethyl benzene - cyclohexane system and ΔH=−13.1 kJ for the m-cresol - m-xylene - cyclohexane system. The results obtained have been discussed from two points of view, that is, the proton-donating power of alcohols and the proton-accepting power of aromatic hydrocarbons.
  • Yuji Ohashi, Hitoshi Iwasaki, Yoshihiko Saito
    1967 Volume 40 Issue 8 Pages 1789-1796
    Published: 1967
    Released: March 27, 2006
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    The crystal structure of the 1 : 1 complex formed between N, N, NN′-tetramethyl-P-phenylenediamine and 1,2,4,5-tetracyanobenzene has been determined by X-rays at room temperature. The crystals are triclinic with one formula unit of the complex in a cell of dimensions: a=7.654 Å, b=8.041 Å, c=7.462 Å, α=96.7°, β=85.9° and γ=101.3°. The space group is P\bar1. The structure has been solved by three-dimensional Fourier and least-squares methods. The component molecules are stacked alternately in infinite columns along the c-axis. The structure does not seem to show the usual π–π interaction between the two aromatic rings, but indicates the n–π interaction localized between the nitrogen atoms of the donor and the cyano groups of the acceptor. From the direct integration of the electron density, the quantity of the charge transfer from the donor to the acceptor has been estimated to be 0.24 in electron units.
  • Haruo Nakayama, K\={o}z\={o} Shinoda
    1967 Volume 40 Issue 8 Pages 1797-1799
    Published: 1967
    Released: March 27, 2006
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    The solubilities of sodium dodecyl sulfate and potassium perfluoro-octanoate in the presence of added salts have been measured as a function of the temperature. The solubility decrease caused by the added salt was remarkable at temperatures a few degrees higher than the Krafft point of a system which contained no salt. The solubility of the solid agent below the Krafft point decreases, approximately inversely proportionally to the concentration of the gegenion as was expected from the solubility product principle, whereas in these experiments the critical micelle concentration (the single-dispersion solubility of a liquid agent), the CMC, decreases inversely proportionally to about the 0.6th power of the gegenion concentration. Hence, the point of the intersection of the solute-solid and solute-liquid equilibrium curves, i. e., the melting point of a hydrated solid agent, shifts to a higher temperature upon the addition of salt. The Krafft-point elevation caused by added salt is explained by the model; the Krafft point is the melting point of a hydrated solid agent, and the formation of the micelle is regarded as a pseudo-phase separation. It is easy to evaluate graphically the Krafft-point elevation in the presence of a 1-1 type salt by applying the above experimental relations.
  • Akio Hosaka, Akira Sugimori, Tsuguo Genka, Gen-ichi Tsuchihashi
    1967 Volume 40 Issue 8 Pages 1799-1803
    Published: 1967
    Released: March 27, 2006
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    The radiolysis of solid malonic acid by 60Co γ-rays has been studied in vacuo at −196°C, − 78°C, and room temperature. All the products were measured after dissolving the irradiated malonic acid in water. The main products were carbon dioxide with G=4.4 and acetic acid with (G=4.5, as was determined by the reverse isotope dilution analysis. The yields of the other products (hydrogen, carbon monoxide, methane, ethane and carbonyl compounds) were very low. These facts revealed that the following reaction takes place selectively:
    (Remark: Graphics omitted.)
    The mechanism of the reaction is discussed with reference to the results of product analyses and ESR.
  • Akio Hosaka, Akira Sugimori, Gen-ichi Tsuchihashi
    1967 Volume 40 Issue 8 Pages 1803-1806
    Published: 1967
    Released: March 27, 2006
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    The C-13 isotope effects in the radiation-induced decarboxylation of several dicarboxylic acids were investigated. Malonic acid showed a C-13 isotope effect of about 2%; this is much greater than those of monocarboxylic acids. The greater isotope effect of malonic acid is attributed to the intramolecular competition of the C-carboxyl bond rupture. Succinic, adipic, and pimeric acid, in which the intramolecular interaction of two carboxyl groups can be expected, gave large isotope-effect values, whereas glutaric and sebatic acid, in which such an effect may be expected to be small, showed lower isotope effects. Analogously, maleic acid (cis isomer) showed a larger isotope effect than did fumaric acid (trans isomer).
  • Teijiro Yonezawa, Isao Morishima, Katsuhiko Takeuchi
    1967 Volume 40 Issue 8 Pages 1807-1813
    Published: 1967
    Released: March 27, 2006
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    The variations in the chemical shifts of proton resonances in some polar compounds in benzene solution, when a portion of protic substances, methanol or trifluoroacetic acid, is added, are determined. It is found that protons of a solute molecule undergo an upfield shift which is enhanced by an increase in the concentration of added protic substances. The protons lynig in proximity to the proton-accepting center of the molecule are more sensitive to this upfield shift than are those far remote from it. The shifts induced by the addition of protic substances to a benzene solution are shown to be applicable to the structural determination; this proves to be useful in obtaining informations about the hydrogen bonding.
  • Masamichi Tsuboi, Fukuko Kuriyagawa, Kimiko Matsuo, Yoshimasa Kyogoku
    1967 Volume 40 Issue 8 Pages 1813-1818
    Published: 1967
    Released: March 27, 2006
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    Proton magnetic resonance spectra have been observed of eight phosphoric acid esters in heavy water solutions. Among these esters, 1-phenyltrimethylene phosphate (1-phenyl-1, 3-propanediol cyclic phosphate) is a new compound. It was shown that the six-membered ring in this compound is fixed in a conformation at room temperature. On assuming that it is a chair form, 1-proton should be on the axial bond and this should be in a gauche relation with respect to the O–P bond around the C1–O1 bond. The proton-phosphorus coupling constant, JHP, in this H-C1–O1–P system was found to be 1.5 cps. The JHP in the CH3OP system was found to be 10.3–10.5 cps, and, therefore, JHP in the trans form is considered to be much greater (∼28.2cps) than that in the gauche form. The JHP the RCH2OP systems were found to be 6.3–7.0 cps, and, therefore, C–R bond in these systems are considered to have a greater chance of taking trans position with respect to the O–P bond around the C–O bond than the chance of taking gauche position.
  • Shin Sato, Terumi Terao, Michiyuki Kono, Shoji Shida
    1967 Volume 40 Issue 8 Pages 1818-1822
    Published: 1967
    Released: March 27, 2006
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    Carbon dioxide and sulfur hexafluoride have been used as electron scavengers in the γ-radiolysis of cyclohexane. The dependence of G(H2) on the concentrations of additives can be interpreted satisfactorily in terms of diffusion-controlled reactions between electrons and the additives. A simple calculation was made using a function proportional to r2exp(−αr2) for the initial distribution of secondary electrons. The distribution constant α and the value of G(electrons) were adjusted to make the calculated curve of G(H2) vs- scanvenger concentration coincide with the observed one. The average initial separation of the secondary electron from the parent positive ion was found to be about 50 Å, and G(electrons) = 3.
  • Masatoshi Hirayama
    1967 Volume 40 Issue 8 Pages 1822-1826
    Published: 1967
    Released: March 27, 2006
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    The ESR spectra of the anion radicals of methyl, ethyl and isopropyl benzoates, and of methyl and ethyl isonicotinates were observed. When the spin densities of these anions were calculated by using McLachlan’s method, the results were in good agreement with the experimental data. It has been found that the electron-withdrawing effect of the ester group is situated between those of the cyano and acetyl groups, and that the ester group may be locked into the benzene plane. Comparatively large splittings due to the α-protons in the ester group were observed. The proton position is defined by the notation:
    (Remark: Graphics omitted.)
    An equation, aCH3H=QOCH3Hρoπ, was assumed, and for these anion radicals values of |QOCH3H| much larger than 27.2 gauss for the C–CH3 hyperconjugation were evaluated.
  • Shigekazu Kumakura, Fujiko Iwasaki, Yoshihiko Saito
    1967 Volume 40 Issue 8 Pages 1826-1833
    Published: 1967
    Released: March 27, 2006
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    The crystal of the equimolar complex between 1, 2, 4, 5-tetracyanobenzene and naphthalene is monoclinic, with space group C2/m, a=9.39, b=12.66, c=6.87 Å, β=107.2 ° and Z=2. The structure was deduced from the hk0 weighted reciprocal lattice and a packing consideration, and refined by the three-dimensional difference synthesis and the block-diagonal least-squares method. The constituent molecules are approximately planar and overlap each other with an average interplanar spacing of 3.43 Å. They are stacked alternately in infinite columns along the c axis. The structure is disordered, with the naphthalene molecules adopting one of alternative orientations with equal probability. The determined structure is consistent with the electronic spectra of the cyrstal.
  • Masanori Nagatani, Tetsuro Seiyama, Minoru Sakiyama, Hiroshi Suga, Sy& ...
    1967 Volume 40 Issue 8 Pages 1833-1844
    Published: 1967
    Released: March 27, 2006
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    The heat capacities of ammonium nitrate were measured between 15 and 410°K for the stable and metastable phases by use of adiabatic- and conduction-type calorimeters. The phase transformations between stable phases; i.e., V–IV, IV–III, III–II and II–I, and the metastable one between IV and II, were all found to be of first-order type. The direct transition between V and II, which is only realized for the sample treated with a minute amount of surface active agent, was ascertained to be typical higher-order type. Heat and entropy of transition of five kinds of transitions were determined. These results conclude that the heat capacity data by Stephenson et al. at low temperature region are much more reliable than the recent values by Eichenauer et al. The possibility of the existence of the seventh phase below 156°K has been proposed.
  • Yuko Hasegawa, Kiyohiko Maki, Tatsuya Sekine
    1967 Volume 40 Issue 8 Pages 1845-1848
    Published: 1967
    Released: March 27, 2006
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    The complex formation of calcium and strontium with sulfate and oxalate ions has been studied in 1 M perchlorate media at 25 °C by a liquid-liquid distribution method. The radioisotopes, calcium-45 and strontium-85 at tracer concentrations were used in conjunction with, thenoyltrifluoroacetone in methylisobutylketone or in carbon tetrachloride containing tributyl-phosphate. The complex formation was determined by a graphical method from the decrease in the extraction of the metal ions with the increases in the concentration of sulfate or oxalate ions in the aqueous phase. The results were explained by the formation of the first and the second complexes, and the stability constants, βn=[MLn2−2n]⁄[M2+][L2−]n, were determined as follows; Sulfate systems, Ca(II): logβ1=1.10, logβ2=1.36, Sr(II): log⁄β1=0.72, logβ2=1.29. Oxalate systems, Ca(II): logβ1=1.66, logβ2=2.69, Sr(II): logβ1=1.25, logβ2=1.90.
  • Eishin Kyuno, Minoru Kamada, Nobuyuki Tanaka
    1967 Volume 40 Issue 8 Pages 1848-1854
    Published: 1967
    Released: March 27, 2006
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    The systematic synthesis of ammine series of chromium (III) complexes has been developed by using aquopentamminechromium(III) nitrate as a starting material. The procedure for the preparation of aquopentamminechromium(III) nitrate was improved to increase the yield. Twenty five sorts of chromium(III) complexes were obtained by the systematic synthesis, of which the procedures for the preparation of eleven sorts of complexes including a new complex, dinitritotetramminechromium(III) bromide, are described. The visible and ultraviolet absorption spectra in aqueous solutions and infrared spectra in solid state of those complexes have been obtained and their structures are discussed.
  • Shoichiro Yamada, Emiko Yoshida
    1967 Volume 40 Issue 8 Pages 1854-1857
    Published: 1967
    Released: March 27, 2006
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    Many compounds of the Co(Aca.R)2 and the Co(Bza.R)2 type have been synthesized, in order to examine the stereochemistry of bis(β-ketoaminato) cobalt(II) complexes (bis(acetylacetone and bis(benzoylacetone-aminato)cobalt(II) complexes are abbreviated as Co(Aca.R)2 and Co(Bza.R)2, respectively, R being an aryl group attached to the nitrogen atom.) and compare it with that of bis (salicylideneiminato) cobalt (II) complexes. The configuration of these cobalt (I I) complexes in non-donor solvents is tetrahedral, but the complexes in pyridine take a tetrahedral, a penta-coordinate or an octahedral configuration, depending upon the ligand. The complexes of the Co(Bza.R)2 type in pyridine take an octahedral configuration, except for Co(Bza.2, 6-X2C6H3)2, where X denotes CH3 and C2H5. On the contrary, Co(Aca.CH3C6H4)2, Co(Aca.2, 6-(CH3)2C6H3)2 and Co(Aca.α-naphthyl)2 in pyridine retain a tetrahedral configuration, while the complexes, such as Co(Aca.C6H5)2 and Go(Aca.ClC6H4)2, take an octahedral configuration with two pyridine molecules bound to the cobalt(II) ion.
  • Mutsuo Kodama, Hide Ebine
    1967 Volume 40 Issue 8 Pages 1857-1861
    Published: 1967
    Released: March 27, 2006
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    The solution equilibria between Eriochrom Black T (BT) and the zinc(II)-NTA or copper(II)-CyDTA chelate were studied spectrophotometrically, and the stability constants and the compositions of 1-to-1 chelates of BT with these metal ions were determined. Under the experimental conditions employed, irrespective of pH, copper(II) forms only a normal chelate, CuD, with BT, the stability constant of which is 1021.98(μ=0.10). Zinc (II), however, forms a normal chelate, ZnD, at pH values lower than 9.00 and a mixed chelate, ZnDX4−, with BT and NTA at pH values higher than 9.00. The stability constant for ZnD was determined to be 1012.76 (μ=0.10) at pH 8.50, in good agreement with the value reported by Schwarzenbach, and that for ZnDX4−, 1015.38 (μ=0.10).
  • Toshiyuki Isobe, Sigeo Kida, Seizo Misumi
    1967 Volume 40 Issue 8 Pages 1862-1863
    Published: 1967
    Released: March 27, 2006
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    The 1 : 1 complexes of lanthanide(III) ions such as La(III), Pr(III), Nd(III), Gd(III) and Er(III) with tris-(salicylidene amino)-triethylenetetramine have been prepared. Among these complexes, the lanthanum(III) complex is unique in infrared spectra and solubility to the solvents; it is soluble in chloroform and nitrobenzene and found to be dimeric in chloroform solution. The other lanthanide(III) complexes are practically insoluble in any available solvents, and are assumed to be polymeric.
  • Shoichiro Yamada, Yoshio Kuge, Kuniko Yamanouchi
    1967 Volume 40 Issue 8 Pages 1864-1867
    Published: 1967
    Released: March 27, 2006
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    Nickel(II) complexes of Schiff bases derived from salicylaldehyde and amines have so far been studied. In the present work, the nickel(II) complexes of N-hydroxyalkyl-salicylideneimines and related compounds are taken up, and the behavior of the hydroxyl group as to its coordination with the nickel(II) ion is examined. Bis(N-hydroxyalky 1-3-methoxysalicylideneiminato)-and bis(N-hydroxyalkyl-salicylideneiminato)-nickel(II) complexes have been prepared in the present work, where R=CH2CH2OH, CH2CH(CH3)OH, C(CH3)2CH2OH and CH2CH2CH2·OCH3. These complexes, except for the complexes with R=CH2CH2CH2OCH3, in the solid state are hexa-coordinated and show paramagnetism corresponding to two unpaired electrons. They are hexa-coordinated in non-donor solvents, except for the nickel(II) complexes with R=C(CH3)2CH2OH, which take a hexa-coordinated configuration in ethanol or methanol, a square-planar configuration in chloroform, and a different configuration in pyridine.
  • Nobuko Matsuoka, Jinsai Hidaka, Yoichi Shimura
    1967 Volume 40 Issue 8 Pages 1868-1874
    Published: 1967
    Released: March 27, 2006
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    Five new complexes, C1-cis(O)[Co(gly)2(en)]Br·3H2O, C2-cis(O)-[Co(gly)2(en)]Br·H2O, trans(N)-K[Co(ox)(gly)2], C1-cis(N)- and C2-cis(N)-Na[Co(ox)(gly)2], have been synthesized. The geometrical isomers of both the [Co(gly)2(en)]+ and the [Co(ox)(gly)2] complex have been separated by ion-exchange column chromatography. The geometrical structures have been determined on the basis of the visible absorption spectra and of the NMR spectra, and from a consideration of the reaction processes of derivation. The visible and near-ultraviolet absorption spectra of a complete series of the sixteen complexes of the [Co(ox)x(gly)y(en)z] type, have been measured and discussed.
  • Haruo Miyata
    1967 Volume 40 Issue 8 Pages 1875-1878
    Published: 1967
    Released: March 27, 2006
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    2-(1, 8-Dihydroxy-3, 6-disulfo-2-naphthylazo)-phcnoxyacetic acid has been synthesized. The acid dissociation constants of the reagent have been determined spectrophotometrically at 25 °C and at an ionic strength of 0.1. The reagent forms a violet 1 : 1 complex with thorium, showing an absorption maximum at 575 mμ in an acidic solution. The apparent stability constant of the thorium complex was measured over the pH range from 1 to 3.5.
  • Yoshio Hori, Takashi Mukaibo
    1967 Volume 40 Issue 8 Pages 1878-1883
    Published: 1967
    Released: March 27, 2006
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    The rate of the reaction between uranium monocarbide and water vapor was investigated in a flow system under the conditions of 53–90°C and 20–120 mmHg. The rate of evolution and the composition of gases were measured by means of a gas chromatograph. The reaction versus time curve was sigmoid-shaped and found to be divided into three parts. Avrami’s equation for nucleation and growth fit the first part. The second part was expressed by a quasi first order reaction. Rate constants for the first and the second parts were found to depend on the water vapor pressure, obeying Langmuir’s adsorption isotherm. The activation energy for reaction and the heat of adsorption for the first part were determined to be 13.0 and 3.9 kcal/mol respectively.
  • Kaoru Hanaya
    1967 Volume 40 Issue 8 Pages 1884-1888
    Published: 1967
    Released: March 27, 2006
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    2-Acetoxy-1-tetralone (VI) and 3-acetoxy-4-chromanone (VII) were reduced with a metal hydride complex and by catalytic hydrogenation; the main products of the reduction were found, to be cis-forms. These results indicate that, in the catalytic hydrogenation, the acetoxyl groups at the C-2 position of VI and at the C-3 position of VII hinder these carbonyl compounds from being adsorbed on the catalyst; also, in the reduction with metal hydride complex, the acetoxyl groups exert a steric hindrance upon the approach of the hydride ion to the carbonyl carbon atom.
  • Akira Misono, Yasuzo Uchida, Taro Saito, Keiichi Uchida
    1967 Volume 40 Issue 8 Pages 1889-1893
    Published: 1967
    Released: March 27, 2006
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    The reactions of 1,3-dienes with acrylates by the use of catalyst systems composed of transition-metal acetylacetonates and triethylaluminum were studied. Butadiene and isoprene react with acrylates to give hepta-2, 5-dienoates and 5- or 6-methylhepta-2, 5-dienoates respectively, by means of the binary catalyst system consisting of cobalt (III) or iron (III) acetylacetonate and triethylaluminum. The effects on this reaction of changing the catalyst concentration, the molar ratio of triethylaluminum to the transition-metal acetylacetonates, and the mixing order of the reagents were examined, as was the difference in catalytic activities between cobalt and iron catalyst systems.
  • Yasukazu Ohkatsu, Takao Hara, Tetsuo Osa, Akira Misono
    1967 Volume 40 Issue 8 Pages 1893-1899
    Published: 1967
    Released: March 27, 2006
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    Peracrylic acid was decomposed by four kinds of catalysts in a benzene solution at 30°C. The order of the catalysts’ effect on the decomposition was: Mn>Co>Fe>Ni; this agreed, except for the reverse order of Co and Mn, with that of the effective catalysts in the oxidation of acrolein (Co>Mn>Fe>Ni). The empirical rate equation,
    −d(CH2=CHCOO2H)⁄dt=k(CH2=CHCOO2H)0.58(catalyst)0.56
    was obtained from the decomposition by Co(acac)3. On the other hand, from the stationary-state treatment of elementary steps adequate to the reaction and some assumptions, and from the experimental data, the following equation was derived:
    −d(CH2=CHCOO2H)⁄dt=1.3×10−1(CH2=CHCOO2H)(Co3+)+9.6×10−3(CH2=CHCOO2H)1⁄2(Co3+)1⁄2
    The above two equations have been confirmed as agreeing with each other over the range of reaction conditions used. The interaction of peracrylic acid with acrolein was carried out in the absence of a catalyst under an oxygen or nitrogen atmosphere. In this case, there was formed a complex consisting of both peracrylic acid and acrolein. The complex was mainly decomposed through the ionic mechanism, but in part through the radical mechanism at a higher temperature, namely, through the homolytic cleavage of its peroxy group, followed by the induced decomposition of peracrylic acid. Furthermore, the formation mechanism of acrylic acid in the oxidation of acrolein was discussed in view of the activation energy of the decomposition of peracrylic acid.
  • Kunio Okamoto, Hajime Kushiro, Issei Nitta, Haruo Shingu
    1967 Volume 40 Issue 8 Pages 1900-1904
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The rates of the bimolecular nucleophilic substitution (SN2 reactions) of phenacyl bromide with sodium para-substituted phenoxides, sodium para-substituted benzoates, and sodium aliphatic carboxylates have been measured in 50% aqueous acetone at 10–70°C. Linear free-energy relationships between the nucleophilic reactivities and basicites (expressed in terms of the pKa’s of the conjugate acids) have been observed in the reactions of para-substituted aromatic nucleophiles, whereas no linear relationships have been seen in the reactions of aliphatic carboxylates except in the cases of sodium acetate, sodium formate, and sodium monochloracetate. An equation, logk2=αpKa+const., has been applied to these reaction series and to the 30 literally-known series of SN2 reactions. The correlation coefficients have then been calculated as a measure of the precision of these linear relationships. Hammett’s ρ values for the reactions of para-substituted aromatic nucleophiles have also been calculated, and the several factors which affect the linear relationships have been discussed.
  • Kunio Okamoto, Issei Nitta, Tetsuo Imoto, Haruo Shingu
    1967 Volume 40 Issue 8 Pages 1905-1908
    Published: 1967
    Released: March 27, 2006
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    The linear free-energy relationships have been examined for 35 SN2 reaction series, including 4 series of the SN2 reactions of alkyl bromides which rates were measured in these laboratories. These results have then been treated using the equation, log(kk0)=rα, where α is a structural constant for methyl, ethyl, n-propyl, n-butyl, i-propyl, i-butyl, and neopentyl groups and where r is a reaction constant. The α values have been estimated as the arithmetic means of the logkSN2 values of the reaction series examined for each alkyl. The correlation coefficients for r’s are greater than 0.960 for all of the reaction series except two. The inapplicability of Taft’s polar and steric substituent constants (σ* and Es) to the SN2 reactivity of these alkyl groups has been discussed.
  • Kunio Okamoto, Teruo Kita, Haruo Shingu
    1967 Volume 40 Issue 8 Pages 1908-1912
    Published: 1967
    Released: March 27, 2006
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    The rate of the bimolecular reactions of a series of ω-chloroalkylbenzenes, C6H5(CH2)nCl(n=1–4), with sodium acetate have been measured in 50 vol% aqueous acetone in the range from 100 to 130°C. The second-order rate constants, k2, have been obtained by measuring the rate of chloride-ion liberation. From the k2 values, i. e., kSN2+kE2, and the olefin percentage in the products, which was determined by measuring the rate of acetic acid formation, the SN2 rate constant, kSN2, and the E2 rate constant, kE2, for each chloride have been calculated. For purposes of comparison, the kSN2 and kE2 values for n-alkyl chlorides, CnH2n+1Cl (n=1–4), in the same solvent at 120°C have been calculated by a similar treatment of the rate in the bimolecular reactions of titled chlorides with sodium acetate. There is an alternation effect on the SN2-rate sequence of the ω-chloroalkylbenzenes, whereas no alternation effect has been observed for the E2 reactions of ω-chloroalkylbenzenes or for the SN2 and the E2 reactions of n-alkyl chlorides. From an examination of these data, together with the results previously reported in the literature, the zigzagging of the rate sequence in the SN2 reactions of ω-substituted alkyl halides has been thought most probably to originate from steric effects. In contrast to the previous observation in the E2 reactions of alkyl bromides with sodium ethoxide, the rate sequence for alkyl chlorides with sodium acetate has been found to be governed by the Hofmann rule.
  • Kunio Okamoto, Teruo Kita, Kiyoshi Araki, Haruo Shingu
    1967 Volume 40 Issue 8 Pages 1913-1916
    Published: 1967
    Released: March 27, 2006
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    Rates in the SN2 and E2 reactions of a series of β-substituted ethyl chloride (RCH2CH2Cl, R=Et, MeO, PhO, Gl, and H) in aqueous solutions have been measured at temperatures ranging from 90 to 150°C, using sodium acetate as a nucleophile. The mild rate-retarding effect of β-subtituents in the SN2 reactions, observed in the rate order, H>Et>MeO>Cl>PhO, may be attributed to the steric effects. In a similar fashion, the retardation of E2 reaction rates by the β-substituents, which is in the rate sequence H>MeO>Et>PhO>Cl, may be ascribed to the steric effects, which outweigh the electronic effects. The β-substituent effects of several other substituents, which are known in the literature, have also been discussed.
  • Kunio Okamoto, Hisayuki Matsuda, Hiroshi Kawasaki, Haruo Shingu
    1967 Volume 40 Issue 8 Pages 1917-1920
    Published: 1967
    Released: March 27, 2006
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    The rates of the reactions of 1, 2-dichloroethane with sodium hydroxide, sodium phenoxide, trimethylamine, pyridine, and sodium acetate have been measured in aqueous solutions at 110 and 120°C. On the assumption that the substitution reaction of 1, 2-dichloroethane produces two equivalents of the chloride ion because of the greater reactivity of the mono-substitution products (β-substituted ethyl chlorides) than that of the starting substrate, while the elimination product from 1, 2-dichloroethane, i. e., vinyl chloride, does not react with the bases under the reaction conditions employed, the kSN2 and kE2 have been calculated from the rate of the chloride-ion liberation and from the number of moles of the base required to react with one mole of the substrate. For a series of kSN2 values there is no linear relation between the rates and the pKa’s of the conjugate acids, whereas a parallelism exists between the kE2 and the pKa. The stronger the base, the more the elimination is promoted.
  • Kunio Okamoto, Suguru Fukui, Haruo Shingu
    1967 Volume 40 Issue 8 Pages 1920-1925
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The kinetics of the reactions of trimethylamine, dimethylamine, methylamine, and ammonia with methyl iodide in aqueous solutions have been investigated at temperatures ranging from 0 to 40°C. Kinetic analyses of the consecutive methylations of dimethylamine and methylamine have been conducted according to the method of French. In the case of ammonia a standard second-order kinetic treatment can be successfully used because of the relative sluggishness of the first stage as compared with the succeeding stages. The observed rates are in the sequence: Me3N>Me2NH>MeNH2>NH3. The factors which affect this rate sequence are discussed.
  • Tetsuo Suami, Seiichiro Ogawa
    1967 Volume 40 Issue 8 Pages 1925-1929
    Published: 1967
    Released: March 27, 2006
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    Starting from epi-inositol, two new inosamines: epi-l and epi-6, and two inosadiamines: myo-4, 6 and streptamine, have been prepared by a replacement of sulfonate group by an azide ion. The nuclear magnetic resonance spectroscopy has established the configurations of the products.
  • Yoshinobu Takegami, Toru Ueno, Kunihiko Masunaga
    1967 Volume 40 Issue 8 Pages 1930-1933
    Published: 1967
    Released: March 27, 2006
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    The reaction of anhydrous nickel(II) chloride with methylhydropolysiloxane has been found to give an active catalyst for the hydrogenation of olefins. These two reagents react readily at 120–170°C, with the evolution of hydrogen, to form a black-colored substance which has been used as the catalyst. The catalytic activity has been found to depend on the amount of hydrogen evolved during the reaction and on the methylhydropolysiloxane : nickel chloride ratio. The most active catalyst has been obtained by using the reagents in the Si : Ni ratio of 25 : 1 and by intercepting the reaction as soon as the hydrogen evolution amounted to 1.0 mol per mole of nickel chloride. Cyclohexane has been successfully used as a solvent. However, the presence of diethyl ether or tetrahydrofuran has considerably deactivated the catalyst. The catalyst deactivated by ether has, though, been highly activated by adding a large excess of water.
  • Kunihiro Ichimura, Masaki Ohta
    1967 Volume 40 Issue 8 Pages 1933-1936
    Published: 1967
    Released: March 27, 2006
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    A new route to aromatic ketenimines is described. The reaction of diphenylmethylenearylamines with chloroform/t-butoxide gave 1,3,3-triaryl-2,2-dichloroaziridines which could be pyrolytically converted to N-aryl-α-chlorodiphenylacetimidoyl chloride. When the 2,2-dichloroaziridines were treated with excess sodium iodide in acetone, aromatic ketenimines were obtained in excellent yields.
  • Akira Terada, Alfred Hassner
    1967 Volume 40 Issue 8 Pages 1937-1940
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    In connection with our studies on introduction of nitrogen functions into steroids we investigated the addition of nitrosyl chloride and of nitryl chloride to 2-chlestene. Addition of nitrosyl chloride to 2-cholestene followed by dehydrohalogenation with pyridine leads to 2-nitro-2-cholestene as the only isolable product. The formation of nitro addition products is not attributable to the reaction of the olefin with nitryl chloride since the latter reacts with 2-cholestene to give mainly 2β, 3α-dichlorocholestane and 3α-chloro-2β-cholestanyl nitrate.
  • Teruzo Asahara, Hideo Kise
    1967 Volume 40 Issue 8 Pages 1941-1945
    Published: 1967
    Released: March 27, 2006
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    The telomerizations of butadiene with its hydrochlorides (1-chlorobutene-2 and 3-chlorobutene-1) in several sorts of solvents in the presence of Lewis acids were investigated. Titanium tetrachloride in ethyl bromide has a considerable catalytic ability at low temperatures and gives telomers with higher average molecular weights than ferric chloride and aluminum chloride at almost the same conversions of reaction. On the other hand, antimony pentachloride gives only a small amount of product with lower average molecular weights. The telomerizations in methylene dichloride and chloroform give almost the same amounts of telomers with molecular weights higher somewhat in the former solvent than the latter. The telomerization in toluene gives primarily the products of Friedel-Crafts reaction, and a small amount of telomers of butadiene with crotyl chloride is obtained. The use of ethyl ether, acetonitrile and acetic anhydride as solvents at low temperatures in the presence of ferric chloride affords poor yields of the telomers in contrast to the cases of halogenated hydrocarbons. In ethyl ether, an appreciable amount of telomers is obtained only at the temperatures above 0°C. The telomers thus obtained have a lower average molecular weight and a larger degree of residual unsaturation than the telomers obtained in halogenated hydrocarbons. The use of nitromethane and nitrobenzene as solvents leads to the formation of an amount of telomers smaller a little than halogenated hydrocarbons. There are scarcely observed differences in the compositions of fractions in 1 : 1 adducts of butadiene and its hydrochloride obtained in the various solvents. The infrared spectra of the higher telomers are almost the same each other and it was concluded that the reactions proceed on the same mechanism irrespective of the variation of solvents.
  • Okitoshi Abe, Hideo Takiguchi, Motonori Ohno, Satoru Makisumi, Nobuo I ...
    1967 Volume 40 Issue 8 Pages 1945-1951
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    A protected cyclic hexapeptide (XVI), cyclo-(diglycyl-ε-benzyloxycarbonyl-L-lysyl)2, was synthesized in three different ways; the cyclization reactions of a protected tripeptide azide, a protected tripeptide active ester, and a protected hexapeptide active ester produced the protected cyclic hexapeptide (XVI) in fairly good yields. The product (XVI) was then converted by hydrogenolysis to the cyclic hexapeptide (XVII), cyclo-(digrycyl-L-lysyl)2. It was found that the cyclic hexapeptide was hydrolyzed slowly by trypsin to a tripeptide diglycyl-lysine, whereas a synthetic hexapeptide, diglycyl-lysyl-diglycyl-lysine, was hydrolyzed very rapidly to the tripeptide.
  • Tatsuaki Yamaguchi, Teruaki Mukaiyama
    1967 Volume 40 Issue 8 Pages 1952-1954
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The reactions of N, N -dimethylbenzamide diethylmercaptole with mercuric compounds (mercuric oxide, mercuric acetate and mercuric cyanide) or lead(IV) compounds (lead dioxide and lead tetraacetate) have been investigated. Mercuric acetate was found to react easily with the amide mercaptole giving N, N-dimethylbenzamide and acetic anhydride with the elimination of mercury ethylmercaptide. In a similar way, mercuric cyanide gave α-dimethylamino phenylmalononitrile in a good yield. Further, it was shown that the amide mercaptole was oxidized by lead dioxide or lead tetraacetate to N, N-dimethylbenzamide and diethyl disulfide. The high reactivity of the amide mercaptole toward heavy metal compounds was discussed in comparison with common mercaptals.
  • Akira Yokoo, Shiro Morosawa
    1967 Volume 40 Issue 8 Pages 1954-1957
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The alternative structure of III, 2-methyl-4,5,7,8-tetrahydro-6(H)-azepino[5,4-d]thiazole (IV) has been found by a study of the NMR spectrum of the corresponding 6-ethoxycarbonyl derivative (V). The structure of 1-ethoxycarbonyl-3-hydroxymethylene-1-azacycloheptan-one (VIII) has also been ascertained by a study of the NMR spectrum and also by its conversion into the methyl derivative (XI).
  • Takashi Amiya, Takeo Shima
    1967 Volume 40 Issue 8 Pages 1957-1960
    Published: 1967
    Released: March 27, 2006
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    Delcosine (lucaconine) and its derivatives have all been shown to lose one mole of water, upon treatment with acetyl chloride, thus giving an anhydro compound. On the basis of the observation of the infrared spectra of anhydro-diacetyldelcosine, anhydro-oxodelcosine, and anhydro-1, 10-didehydro-oxodelcosine, it may be concluded that, in each compound, dehydration takes place between two tertiary hydroxyl groups, with a ketone carbonyl group being formed. Based on a tentative structure for delcosine proposed by Marion and his co-workers, structures for anhydro-diacetyldelcosine and anhydro-oxdelcosine are proposed. On hydrogenation over platinum in acetic acid, anhydro-diacetyldelcosine yielded anhydro-dihydro-diacetyl-delcosine. Anhydro-oxodelcosine was inert under these reduction conditions. On the basis of these experimental results, a possible mechanism of this novel hydrogenation is proposed. The ultraviolet spectrum of anhydro-diacetyldelcosine, with a new type of chromophore, is also shown.
  • Takeo Saegusa, Sadao Kitagawa, Takashi Ueshima
    1967 Volume 40 Issue 8 Pages 1960-1964
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Reactions of n-butyraldehyde caused by tris(trimethylsiloxy)aluminum were examined and compared with those caused by aluminum t-butoxide. In the Tishchenko reaction of aldehyde caused by aluminum t-butoxide, the t-butoxy group was first transferred from aluminum to the carbonyl group of n-butyraldehyde to produce t-butyl n-butyrate. On the other hand, we observed no formation of trimethylsilyl n-butyrate by the transfer of the trimethylsiloxy group to n-butyraldehyde. However, esters of the n-butyric acid of n-butanol and the glycol derived from the aldol of n-butyraldehyde were found in the system with tris(trimethylsiloxy)aluminum: their formation was ascribed to the aluminum alkoxide species which was first formed between tris(trimethylsiloxy)aluminum and the aldol of n-butyraldehyde. The above assumption has been supported by the finding that aluminum t-butoxide caused the Tishchenko reaction of benzaldehyde, producing benzyl benzoate almost quantitatively, whereas tris(trimethylsiloxy)aluminum did not cause any change because aldol condensation was impossible for benzaldehyde.
  • Teng-yueh Chen, Hiroshi Kato, Masaki Ohta
    1967 Volume 40 Issue 8 Pages 1964-1966
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The addition of azetidine to α,β-unsaturated esters and to acrylonitrile was studied. Azetidine was condensed with ketones to give the corresponding enamines.
  • Toshio Mukai, Haruki Tsuruta, Yoshitaka Momotari
    1967 Volume 40 Issue 8 Pages 1967-1972
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    From the point of view of the nucleophilic substitution, the Grignard reaction of 1,3-diazaazulene (I) was investigated using phenyl magnesium bromide and t-butyl magnesium chloride. Substitution occurred at 4- and/or 6-positions of I and 4-phenyl-4H-(II), 4-t-butyl-4H- (VIIIa) and 6-t-butyl-6H-cycloheptaimidazole (VIIIb) were isolated respectively. The NMR and UV spectra of these products were discussed. Of the products, II and VIIIb afforded 4-phenyl-(III) and 6-t-butyl-1, 3-diazaazulene (XI) by dehydrogenation.
  • Sumio Umezawa, Kuniaki Tatsuta, Tsutomu Tsuchiya, Eiichi Yamamoto
    1967 Volume 40 Issue 8 Pages 1972-1974
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The introduction of a phosphate group into the 3-amino-3-deoxy-D-glucose moiety of kanamycin, a useful antibiotic, has been described. Tetra-N-anisylidene kanamycin was treated with diphenyl phosphorochloridate. Hydrolysis of the product followed by hydrogenolysis afforded kanamycin-6′-phosphate in a good yield. An alternative phosphorylation of kanamycin via tetra-N-carbobenzoxykanamycin to hexa-O-acetyl-tetra-N-carbobenzoxy-6′-diphenylphosphoro-kanamycin was described, however, the removal of the all protecting groups except the phosphate group encountered a difficulty.
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