Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 41 , Issue 4
Showing 1-50 articles out of 59 articles from the selected issue
  • Tsutomu Kagiya, Y\={u}z\={o} Sumida, Tokuji Inoue
    1968 Volume 41 Issue 4 Pages 767-773
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    A quantitative study has been made of the measurement of the electron-donating nature and the electron-accepting nature of various liquid organic compounds. The position of the O–D or C=O absorption band of a liquid compound which contained a small quantity of methanol-d or of acetophenone was measured by means of an infrared spectrophotometer. The relative magnitude of the electron-donating nature or of the electron-accepting nature of the compound was compared by a measurement of the perturbation which it produced on the O–D vibrational band of methanol-d or on the C=O vibrational band of acetophenone. The electron-donating power or the electron-accepting power of a compound is defined as the relative difference (counted as wave numbers) of the O–D or the C=O absorption band observed in the compound from that in benzene. From the results, it was found that, in a homologous series, the electron-donating power decreased with an increase in the ionization potential in the gaseous phase, or with an increase in the pKb value in the liquid phase, and that it increased linearly with the co-ordination power to diethyl zinc. It was also found that the electron-accepting power increased with an increase in the electron affinity in the gaseous phase and decreased with an increase in the pKa value in the liquid phase. Moreover, the various liquid organic compounds, classified into four typical groups, were considered on the basis of their electron-donating and electron-accepting power.
  • Tsutomu Kagiya, Y\={u}z\={o} Sumida, Tokuji Inoue
    1968 Volume 41 Issue 4 Pages 773-778
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The nucleophilic solvation to a deuterium atom in a methanol-d molecule has been quantitatively studied by using the infrared spectroscopic data of the O–D vibrational band. The position of the O–D band did not change in spite of the variation in the methanol-d concentration in solutions of a single solvent, whereas the area of the O–D peak changed in proportion to the first-order of the methanol-d concentration. From these results, it has been concluded that the area of the O–D band corresponds to the concentration of the methanol-d solvated. In a binary solvent system, which consisted of components with substantial differences in the electron-donating power, two positions of the O–D peak were observed at positions identical to those in the component examined in a single solvent system, and the area of each O–D peak changed with the composition of the system. These results led to the conclusion that the nucleophilic solvation of each component in the binary system took place competitively and individually. From the quantitative treatment of the results on the basis of the theory of chemical equilibrium, the equilibrium constant of the nucleophilic solvation of a solvent to methanol-d was calculated. The following empirical formula was obtained between the electron-donating powers and the nucleophilic equilibrium constants of various solvents:
    (Remark: Graphics omitted.)
  • Tsutomu Kagiya, Y\={u}z\={o} Sumida, Tokuji Inoue
    1968 Volume 41 Issue 4 Pages 779-782
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    This is the third paper of a series in which the behavior of nucleophilic solvation is investigated by a measurement of the position and the area of the O–D vibrational band of methanol-d. In a binary solution which consisted of two components remarkably different in electron-donating power, the relation between the mol fraction (n1) of the S1 component and the area fraction (n1) of S1 was not a straight line, but a concave or convex curve. This fact suggests that a component co-ordinates selectively to a deuterium atom in a methanol-d molecule. The following definition of the selectivity of nucleophilic solvation to methanol-d as a cation model of the S2 component to the S1 component is proposed:
    (Remark: Graphics omitted.)
    The selectivity of the S2 solvent to the S1 solvent was considered in detail in connection with the equilibrium constant of the nucleophilic solvation to methanol-d of the solvent; the selectivity was also found to be defined as the ratio of the equilibrium constants of the solvents used. Since there was a correlation between the equilibrium constants and the electron-donating powers, it was concluded that the selectivity of an S2 solvent to a standard solvent, S1 could be quantitatively estimated by measuring only the position of the O–D vibrational band of methanol-d in each solvent.
  • Takayuki Fueno, Okitsugu Kajimoto, Junji Furukawa
    1968 Volume 41 Issue 4 Pages 782-785
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The equilibrium constants for the formation of silver ion complexes of various vinyl compounds in water were determined at 25°C by the distribution method. It has been found that the equilibrium constants obtained are closely related to the Hammett sigma meta values of the relevant substituents, the reaction constant being ρ=−5.07 with the correlation coefficient r=0.974. The results have been interpreted in terms of the inductive effect of the substituents as the most dominant contribution to the stabilities of these complexes.
  • Takayuki Fueno, Okitsugu Kajimoto, Tadashi Okuyama, Junji Furukawa
    1968 Volume 41 Issue 4 Pages 785-790
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The equilibrium constants, K, for the formation of 1 : 1 Ag+ - alkenyl alkyl ether complexes were measured in the temperature range 10 to 30°C by the gas chromatographic method. It has been found (1) that cis isomers have the values of K several times greater than those of the corresponding trans isomers, (2) that the K-value tends to diminish with the increasing degree of β-substitutions, (3) that, in a series of cis ethers, K increases as the β-alkyl substituent becomes bulkier, and (4) that the variation of the alkoxy groups causes little change in the K-value. The difference in the K-values between the cis and trans complexes is found to be ascribable mainly to their difference in the enthalpy changes, ΔH, accompanying the complexation. These trends have been discussed on a thermodynamic ground in comparison with those already noted for olefins.
  • Shoichi Kondo, Eijiro Tagami, Kazuyoshi Iimura, Masatami Takeda
    1968 Volume 41 Issue 4 Pages 790-795
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Effect of solvent on the coupling and magnetic shielding constants of meso and racemic 2,3-dichlorobutanes has been examined using proton magnetic resonance (PMR). The iterative method of spectrum analysis is applied to the simple sub-state in order to improve the computation speed and the computer capacity. The variations in the coupling constants for the meso configuration are to some extent correlated with the population as a function of dielectric constant ε of solvent using an Onsager model. The coupling constants of the racemic configuration were almost independent of the solvent dielectric constant. The estimated chemical shift dependence on ε of the reaction field does not adequately describe the experimental data.
  • Shigeya Niizuma, Michio Okuda, Masao Koizumi
    1968 Volume 41 Issue 4 Pages 795-799
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Nature of acridine anions produced by the addition of alkali metals to the tetrahydrofuran solutions of acridine has been studied by means of ESR and VU spectra. In excess of acridine (A), a green species G is produced. This has been identified as ANa+ (or AK+ etc.). ANa+ gives under suitable conditions, ESR spectra with hfs consisting more than fifty lines. This species reverts to acridine upon addition of a small quantity of water or ethanol. With the fall of temperature, the intensity of ESR spectra of G decreases remarkably and accompanied with it, UV spectra of G also decline with no change of the spectral shape, logIvs. 1/T plots where I is either the intensity of UV absorption or of the ESR signal are satisfactorily linear; this has been interpreted to be due to a large equilibrium constant of the process, 2A Na+\ ightleftarrows(Na+A)2 in which (Na+A)2 is a colorless diamagnetic substance. This interpretation has led to the value of enthalpy of dissociation of (Na+A)2 as ca. 14 kcal. When sodium is in excess, a diamagnetic violet species is produced. This has been assigned as Na+A2−Na+. The chemical processes pertaining to ANa+ and Na+A2−Na+ can be summarized as follows:
    (Remark: Graphics omitted.)
  • Takayuki Yano, Kenji Kuratani
    1968 Volume 41 Issue 4 Pages 799-802
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Equimolar mixtures of CH4 and CD4 were pyrolyzed at 1560°K by a reflected shock wave. From the isotope distribution of H2, HD and D2 which are components of the product in early stage, the initiation step of methane pyrolysis is concluded to be the splitting to a methyl radical and a hydrogen atom.
  • Kunitoshi Shimizu, Manabu Sen\={o}, Hiroshi Nozaki
    1968 Volume 41 Issue 4 Pages 802-809
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The rectifying properties of liquid junctions of polyelectrolyte solutions are examined and discussed. In the case of liquid junctions between aqueous solutions of poly(styrene-sulfonic acid) and poly(2-vinyl-N-n-butylpyridinium hydroxide), the rectification effects greatly depend on the concentrations of the polyelectrolytes and on the frequencies of the voltages applied, that is, rectification effects can not be found when the concentrations of polyelectrolytes are lower than 0.68×10−3 equivalents per liter and when the frequencies of the alternating voltages are higher than 200 cps. The mechanism of rectification can be explained to some extent by a semiconductor analogy. In the case of liquid junctions between poly(styrene-sulfonic acid) and poly(2-vinyl-N-n-butylpyridinium bromide), the static current versus voltage curves have strong hysteresis loops. The rectification effects can be slightly observed when alternating voltages with frequencies lower than 100 cps are applied. In this case, however, the mechanism of rectification can not be explained by the semiconductor analogy.
  • Susumu Kinumaki, Muneteru Kozuka
    1968 Volume 41 Issue 4 Pages 809-813
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The infrared absorption spectra of gaseous and liquid CF3CHF2 were examined in the region from 500 to 60 cm−1. The Raman spectrum of the liquid at room temperature was also photographed. In the gas-phase spectrum, bands were observed at 414, 363, 306, 246, 216 and 82 cm−1. The contour of the medium-intensity band at 82 cm−1 was consistent with that to be expected for torsional oscillation. This frequency would correspond to a triple cosine barrier of 4.4 kcal/mol.
  • Yoshitomo Iwakami, Masao Takazono, Toshikazu Tsuchiya
    1968 Volume 41 Issue 4 Pages 813-817
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    In order to get information about the mechanism of the thermal decomposition of hexamethylene tetramine (hexa), hexa was decomposed thermally in a vacuum vessel, and the composition of the gas thus produced was determined with a mass spectrometer. The main products found were ammonia and a carbon-rich solid residue. The carbon in the carbon-rich residue seems to act as a catalyst for the decomposition.
  • Takayuki Fueno, Itaru Matsumura, Tadashi Okuyama, Junji Furukawa
    1968 Volume 41 Issue 4 Pages 818-823
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The rates of hydrolysis of various ring-substituted phenyl vinyl ethers, CH2=CHOC6H4X, have been measured in 80 : 20 dioxane-water containing hydrochloric acid as catalyst. The ring substituents investigated include H, p-CH3O, m-CH3O, p-CH3, m-CH3, p-Cl and m-Cl. The reaction was first order with respect to both the acid and the ethers. It has been found that the effect of substituents on the hydrolysis rates obeys the Hammett ρσ relationship with the reaction constant ρ=−2.21 at 35°C. These results are compatible with the previous conclusion that the acid-catalyzed hydrolysis of alkenyl ethers involves the rate-determining protonation of the ethers at their β-carbon atom, to form intermediate oxycarbonium ions. It has been shown that the observed substituent effect can be rationalized from the π-electronic energy changes of the ethers on protonation, which have been calculated by an empirical molecular orbital method.
  • Shoichi Sato, Yukio Yoneda
    1968 Volume 41 Issue 4 Pages 824-827
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The kinetic factors for phosgene synthesis over thermal and irradiated sucrose carbons were examined in particular regard to their dependences on the heating temperature and irradiation. Gamma-irradiation on carbons prepared at 900 or 1000°C produced new active sites with EA of 11–12 kcal/mol. An explanation is suggested of the effects of heating temperature and irradiation on the catalysts; the catalytic activity is most reasonably related to the degree of growth of the network structure of carbons. In the case of carbons prepared by heating at 900 or 1000°C and having the structure grown to the largest extent, a high dose of gamma-rays presumedly destroys most efficiently the thermally generated active sites and forms sites with a high activation energy. Free radicals and peripheral atoms which also comprise characteristics of amorphous carbons seem to behave independently of catalytic activities and are supposed to have no direct relation to the activities.
  • Takehiko Chiba, Yoshinobu Kakiuchi
    1968 Volume 41 Issue 4 Pages 828-832
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Deuteron spin lattice relaxation time T1 and the reorientation rate of D2O have been measured at various temperatures on a single crystal of Ba(ClO3)2D2O by transient nuclear magnetic resonance method. Temperature dependence of T1 is similar to that of corresponding proton resonance but three to four orders of magnitude smaller than the latter. From the slope of logT1 vs. 1/T curve, activation energy of reorientation of D2O of 6.5–6.8 kcal/mol is obtained in agreement with that from line width transition. Theoretical values of T1 minima were in good agreement with the observed. Direct measurement of reorientation rate is made by observing a signal recovery from saturation of one of the two deuteron sites of D2O due to the exchange with unsaturated spins at the other site. The Arrhenius plot of the reorientation rate down to −170°C determined in this manner smoothly connects to that derived from the line width transition. A revision of the previous treatment of line width change is described and the reorientation rates of Ba(ClO3)2D2O are re-evaluated according to this method. A satisfactory agreement is found among the conclusions from the three different types of experiment, T1, the line width transition and the directly measured reorientation rate. The motion is a random reorientation of D2O with a rate governed by an activation process of 7 kcal/mol.
  • Tadayoshi Tanei
    1968 Volume 41 Issue 4 Pages 833-837
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Benzene adsorbed on silica gel was irradiated at 77°K with ultraviolet light. Three kinds of samples, with different degree of adsorption, were examined. ESR spectra were strongly dependent on the amount of benzene adsorbed and three different spectra were observed; (1) six-line spectrum with a splitting value of 6 gauss, assigned to phenyl radical, (2) seven-line spectrum with a splitting value of 4.5 gauss, assigned to benzene cation radical, and (3) apparent nine-line spectrum with 2.4 gauss splitting due to benzene dimer cation radical. Upon raising temperature, benzene cation radical was found to transform into benzene dimer cation radical. In UV-irradiated benzene-alumina system, cyclohexadienyl radicals were observed in addition to the ion radicals. It is suggested that the above reaction may be occurred by two photon absorption process involving the excitation of triplet benzene.
  • Mitsumasa Miyazaki, Yoshiki Moriguchi, Keihei Ueno
    1968 Volume 41 Issue 4 Pages 838-843
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    1,2,3-Triaminopropane-N,N,N′,N′,N″,N″-hexaacetic acid (TAPHA) was synthesized by the carboxymethylation of 1,2,3-triaminopropane. The acid dissociation scheme of the ligand was studied by means of potentiometric titration, infrared absorption spectroscopy and proton nuclear magnetic resonance spectroscopy. It is found that TAPHA exists as a zwitter ion in aqueous solution, in which protons attach to each nitrogen atom of 1- and 3-carbon, and that the dissociations of first four and the last two steps correspond to the dissociations of carboxylic protons and ammonium protons, respectively. The stepwise proton dissociation constants of the ligand is determined as pK1≈2, pK2=2.43, pK3=3.52, pK4=4.30, pK5=8.26 and pK6=9.88 (μ=0.1, 25°C).
  • A. P. Bhargava, Y. K. Gupta
    1968 Volume 41 Issue 4 Pages 843-849
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    A kinetic study of the oxidation of As(III) by peroxydisulphate catalyzed by Cu(II) has been made. The rate has been measured by estimating As(III) by the permanganate. The data follow the rate expression,
    (Remark: Graphics omitted.)
    A chain mechanism has been suggested in which the decomposition of peroxydisulphate is the chain initiating step. Cu(II) and As(III) participate in the chain propagating steps. Allyl acetate and Mn(II) inhibit the reaction. The mechanism also involves a complex formation between Cu(I) and As (III) with an equilibrium constant, K2, having a value of about 1475 M−1at 35°C. Energy and entropy of activation have been found to be 24190 calories and +10.46 e. u. respectively.
  • Shuichi Hamada, Ryuji Sato, Toshiaki Shirai
    1968 Volume 41 Issue 4 Pages 850-854
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The contents of some minor elements in copper-bearing ores from the Fujimi ore deposit No 5, the Hitachi mine, were determined. The selenium content in 46 samples was found to vary from 0.5 to 117 ppm. Though selenium seems to be concentrated in the ores rich in chalcopyrite, that is not always the case, as there are pyrite-rich ores with higher selenium contents than those rich in chalcopyrite. The average value of the atomic ratio of Se/S in the pyrite ores was calculated to be 3.48×10−5; this value was larger than those found for the ores from the Minenosawa and the Chichibu mines, and about the same as those found for the ores from the Nakase, the Ashio, and the Hanaoka mines. The variations with depth in the atomic ratios of Se/S and Co/Ni are closely related to each other. The atomic ratio of Se/S increased with an increase in that of Co/Ni. It has been concluded that selenium is concentrated in the pyrite ores of the high-temperature-type rather than in those of the low-temperature-type. The mercury content was small in general, but a large content of mercury was observed at the depth where the values of the atomic ratios of Se/S and Co/Ni were at their maxima.
  • Takashi Komorita, Jinsai Hidaka, Yoichi Shimura
    1968 Volume 41 Issue 4 Pages 854-862
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Several planar bis(amino-acid-amidato) complexes of nickel(II) and palladium(II) have been newly synthesized and characterized mainly spectroscopically. The geometrical structures of these [M(N)4]-type complexes have been determined: palladium(II) produced both cis and trans complexes with L-alanine- and L-leucine-amidate ligands, while nickel(II) did only trans forms with glycine-, L-alanine- and L-leucine-amidates. Nickel(II) also produced cationic complexes, Ni(L-alanine-amide)2SO4 and its glycine amide analogue. The circular dichroism spectra and rotatory dispersion of the complexes containing optically active amino acid amide have been measured and discussed as for the assignments of the ligand field absorption bands of the diamagnetic planar complexes. A good correspondence was observed between the circular dichroism spectra of the nickel(II) and the palladium(II) complexes.
  • Hide Saito, Junnosuke Fujita, Kazuo Saito
    1968 Volume 41 Issue 4 Pages 863-874
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Absorption bands, especially metal to amine charge transfer bands of bipyridyl- and phenanthroline-tetracarbonyl chromium (0), molybdenum (0) and tungsten (0) are shifted in various solvents by less than 4500 cm−1. The shift is discussed in accordance with McRae’s equation, which was derived with the point-dipole approximation. The solvents can be classified into two groups, the alcohol and the ester group. When three constants corresponding to (1) the interaction between induced dipoles of the solute and of the solvent, (2) the interaction between permanent dipole of the solute and induced dipole of the solvent, and (3) the interaction between permanent dipoles of the solute and of the solvent, are duely chosen for the two groups of solvent individually, the experimental values are satisfactorily accounted for. Short range interactions, such as hydrogen bonding can be ignored.
  • Fumiaki Kai
    1968 Volume 41 Issue 4 Pages 875-882
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The particular reactivity of basic amino acids in presence of mercury(II) perchlorate gives white amorphous products (by X-ray powder diffraction). The structures of the products may be considered to be [Arg-Hg]ClO4·Hg(ClO4)2, [His-Hg]ClO4·Hg(ClO4)2 and [Lys-Hg]ClO4·Hg-(C1O4)2 on the bases of elemental analytical data and of infrared patterns showing the absorption bands of νas(Hg–O), ν(Hg–N) and perchlorate ions. The applicability of this peculiar reactivity to the separation and photometric determination of basic amino acids has been studied. The above mentioned products were obtained selectively as a mixture from a mixture of about twenty kinds of amino acids. The isolation of the mixture into each product could be performed satisfactorily by utilizing the different solubilities of the products in 10 N acetic acid containing sodium or potassium chloride (3.3 W/V %), and in an aqueous sodium hydroxide solution. Although the products showed characteristic ultraviolet absorption curves differing from those of the components, there were no absorption maxima in any case. The calibration curves, which followed Beer’s law, could be obtained at any proposed wavelength. By using the calibration curves thus obtained, a very small amount of each basic amino acid could be determined spec-trophotometrically in the 220–250 m/μ region, within detection limits of about 10−5–10−4M. Constant absorbancies could be attained in the pH range of 1.5–10.7 of the sample solutions.
  • Goro Wada
    1968 Volume 41 Issue 4 Pages 882-888
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The formation constants of FeCl2+ and FeCl2+ have been measured in dimethyl sulfoxide (DMSO) containing Fe(ClO4)3, NaCl, HClO4 and NaClO4. Some spectrophotometric methods giving the formation constants and molar extinction coefficients of the complexes were developed and gave, on the average, logK1=3.62 and logK2=2.10, at 0.02 M HClO4 and an ionic strength of 0.10 M at 25°C. It is rather surprising that these values are only slightly larger than those in N-methylacetamide, which is expected, however, to give much smaller values than DMSO, due to its extraordinarily large dielectric constant. The species formed between Fe(III) and Cl ion is reasonably supposed to be a true complex bonded directly with each other and not an ion-pair association product. At higher concentrations of Fe(III), formation of polynuclear complexes can occur.
  • Niro Matsuura, Nobuyoshi Shinohara
    1968 Volume 41 Issue 4 Pages 888-892
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Radiation-induced oxidation of cysteine in an acid medium was studied by measuring the hydrogen yields at an initiation stage of radiolysis. In the deaerated system G(H2)=4.0 along with the G(–CySH)=7.1 were observed and the results can be interpreted in terms of the yields of primary radicals from the radiolysis of water in 0.8 N sulfuric acid medium. From stoichio-metric view point it is predicted that the radiolysis takes place through cysteine radical as intermediate to form cystine. In the aerated system on the other hand, the radiolysis of cysteine is much complicated. For a possible explanation satisfying all the G values obtained, 10.5 in the disappearance of cysteine, 4.0 in the formation of hydrogen peroxide and 0.4 in the hydrogen, the air oxidation of cysteine caused by the radicals, HO2 and OH which produce H2O2 and O2 by the radical recombination, is proposed as mechanism. The radiolysis of cysteine is greatly reduced by complexation with metallic ion as biscysteinatocobaltate(III) complex. The absence of hydrogen abstraction from cysteine by H atom, the isolation of cysteine from a ligand site and the extraordinary high G values in the disappearance of optical absorption of the complex can be cited as characteristics in the radiolysis of the biscysteinatocobaltate(III) complex. The intramolecular redox of the complex into Co(II) ion and cysteine is a best fit mechanism as over all reaction in the radiolysis of the biscysteinatocobaltate(III) complex.
  • Tetsuya Ogura, Takeshi Hamachi, Shinichi Kawaguchi
    1968 Volume 41 Issue 4 Pages 892-896
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Crystalline 1 : 1 and 1 : 3 complexes of allylamine and propylamine with copper(I) chloride and bromide were synthesized in vacuo. Equilibrium vapor pressures of these complexes were measured at several temperatures and the enthalpy of ligation of each amine molecule was determined. Both the thermochemical and infrared absorption data indicate that in the 1 : 1 complexes of allylamine the ligand molecule serves as a bidentate, but in the 1 : 3 complexes the second and third ligand molecules link to the metal only through the amino nitrogen atom.
  • Sueo Machi, Takashi Sakai, Fujio Suganuma, Tsutomu Kagiya
    1968 Volume 41 Issue 4 Pages 897-903
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The bulk polymerization of ethylene was carried out under mild conditions, i. e. pressures of from 183 to 400 kg/cm2 and temperatures of from 30 to 140°C, using azobisisobutyronitrile as an initiator. In polymerization at the low temperature of 40°C, both the polymerization rate and the molecular weight of the polymer formed increased with the reaction time. At the above temperature, the polymerization rate was shown to be proportional to the amount of initiator, and the molecular weight was found to be independent of it. Furthermore, both the polymerization rate and molecular weight were found to be proportional to the 2.5th power of ethylene fugacity. The dependencies of the polymerization rate and the molecular weight on the reaction time decrease with the rise in reaction temperatures from 30 to 100°C. A kinetical discussion indicated that the rate of termination is almost zero at 30–40°C, but that it increases with the temperature. The polymerization rate and the molecular weight were shown to be proportional to the 0.8 and 0.2th powers of the amount of the initiator. The activation energy of the initiation reaction was evaluated to be ca. 27 kcal/mol.
  • Etsuro Echigoya, Mitsuo Masai, Kiyoshi Morikawa
    1968 Volume 41 Issue 4 Pages 904-909
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The oxidation of propylene is studied in an excess-propylene atmosphere under pressure, using an inert fluidized bed reactor. The effects of the temperature, the pressure, and the concentration of oxygen on the reaction were examined. The so-called “negative temperature coefficient” is clearly observed with relation to the rate of the oxidation of propylene and the rates of the formation of acetaldehyde, propylene oxide, acrolein, carbon monoxide, methane, and ethylene. Therefore, the reaction courses involving these may be regarded as radical-chain reactions. Little effect of the pressure is observed. The molar fraction of oxygen exerts a profound effect on the yields of acetaldehyde, propylene oxide, and acrolein.
  • Mitsuo Masai, Etsuro Echigoya, Kiyoshi Morikawa
    1968 Volume 41 Issue 4 Pages 910-919
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The mechanism of the oxidation of propylene is studied through the addition of t-butyl hydroperoxide, acetaldehyde, or propionaldehyde to the reactant (propylene and oxygen), and also through the direct addition of the products of the (C3H5Br+O2 or CH3CHO+O2) reaction to propylene. The following conclusions are reached: acetaldehyde and not propionaldehyde is responsible for chain-branching, acetaldehyde is formed from the allyl peroxy radical alone, propylene oxide is formed mainly by the reaction of the acetyl peroxy radical with propylene, the allyl peroxy radical probably contributes to the formation of propylene oxide, propionaldehyde, and acrolein in an equal extent, and the recombination of radicals is highly retarded in this propylene-excess system. On the basis of the data obtained, a plausible reaction scheme is proposed.
  • Mitsuo Masai, Etsuro Echigoya, Kiyoshi Morikawa
    1968 Volume 41 Issue 4 Pages 920-928
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Reaction-rate equations are derived for oxygen, acetaldehyde, propylene oxide, carbon monoxide, and ethylene on the basis of a plausible reaction scheme. These rate equations are shown to fit the experimental results obtained using a flow-type reactor. It seems most reasonable to conclude that the above reaction mechanism is correct. The type of flow of the reactant gas through the reactor used in this work can be practically regarded as a plug flow from the measurements of the resisdence time distribution using the pulse-tracer method.
  • Yoshio Baba
    1968 Volume 41 Issue 4 Pages 928-931
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The reactions of triethylaluminum and its various ether adducts with α,β-unsaturated ketone, aldehyde, ester, and methyleneanthrone have shown that the addition occurs mainly at the 1,2-positions of the carbonyl function, and not at the 1,4-positions as has been observed in the Grignard reaction. The mode of addition was discussed in view of the reactivity of the organometallic compound and the steric factor of the unsaturated carbonyl compounds.
  • Kazuaki Kawamoto, Yoshiharu Nishimura, Teruo Hiraki
    1968 Volume 41 Issue 4 Pages 932-936
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    In order to determine whether the condensing activity of reduced copper is affected by the mode of preparation of the catalyst, the condensation of isopropyl alcohol to isobutyl methyl ketone, diisobutyl ketone, and isobutylmethylcarbinol was studied with catalysts prepared in different ways. It was found that the copper catalyst obtained by the hydrogen treatment of the oxide prepared from copper nitrate and an excess of sodium hydroxide was the most suitable catalyst for the condensation of isopropyl alcohol to isobutyl methyl ketone and diisobutyl ketone, and that the copper catalyst prepared with potassium carbonate was the most suitable catalyst for the dehydrogenation of isopropyl alcohol to acetone with no side reaction.
  • Noboru Sugiyama, Masamoto Akutagawa, Hiroshi Yamamoto
    1968 Volume 41 Issue 4 Pages 936-941
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    A bright green light is observed on the treatment of a solution of 2,3-dimethylindole (I) and its hydroperoxide (II) in dimethyl sulfoxide (DMSO) with alkali (potassium t-butoxide or granular potassium hydroxide) under streams of oxygen and hydrogen respectively. The change in their ultraviolet and fluorescent spectra with the time and the chemiluminescent spectra is measured. The compound II is concluded to be the reaction intermediate of I; it decomposes to yield an excited singlet state of an o-acetamidoacetophenone anion (III*), a light emitting species in this reaction. The investigation, then extended to four 5-substituted-2,3-dimethylindoles, revealed that three of them displayed chemiluminescence through the same mechanism as in the case of I.
  • Yoshiharu Izumi, Tadashi Tanabe, Shinichi Yajima, Masami Imaida
    1968 Volume 41 Issue 4 Pages 941-943
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The asymmetric hydrogenation catalysts were prepared from the Raney nickel catalyst by modifying it with Ls-3,3-dimethyl-2-hydroxybutyric acid and the corresponding amino acid, L-t-leucine, which have most methyl groups at the β-position. The asymmetric activities of the catalysts were measured by the hydrogenation of the methyl acetoacetate to methyl 3-hydroxybutyrate. The asymmetric activity of the catalyst modified with an aqueous solution of Ls-3,3-dimethyl-2-hydroxybutyric acid was very low, and the direction of asymmetric activity at pH 5.0 was inverted by the temperature of the modifying solution. However, there was a high asymmetric activity in the catalyst modified with L-t-leucine, and this activity was not so influenced by the temperature of the modifying solution. The aysmmetric activities of catalysts modified with α-hydroxy acids and the corresponding amino acids reported in this paper and the previous papers are compared, and the effect of the bulk of the α-alkyl substituent of the modifying reagent upon the asymmetric activity of the catalyst is discussed.
  • Takayuki Suga, Tsuyoshi Shishibori, Tamon Matsuura
    1968 Volume 41 Issue 4 Pages 944-948
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    1-Hydroxy-p-menth-3-en-2-one (1) was prepared from α-terpinene by the t-butyl chromate oxidation, trans- and cis-p-Menth-3-ene-1,2-diols (4 and 5), 1-hydroxyisocarvomenthone (2), and 1-hydroxycarvomenthone (3) were also prepared from the compound 1 by lithium aluminum hydride reduction or by hydrogenation. The configurations of these compounds, 1–5, were identified on the basis of chemical evidence, and then the preferred conformation was determined by infrared spectroscopy on the basis of the conception of intramolecular hydrogen bonding. 1 and 2 were found to exist predominantly in the hydrogen-bonded conformations, 1a and 2a, respectively. With respect to 3, the existence of the conformational equilibrium, 3a\ ightleftharpoons3b, was demonstrated by the presence of the free and bonded hydroxyl bands. Moreover, 4 and 5 were proved to take the preferred conformations of 4a and 5a respectively.
  • Naomichi Furukawa, Shigeru Oae
    1968 Volume 41 Issue 4 Pages 949-953
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The alkaline fusion of 2-chlorophenyl phenyl sulfone afforded phenol, benzene and chlorobenzene. The initial step of the reaction appears to be the aromatic SN2-type replacement of chlorine to form 2-hydroxyphenyl phenyl sulfone upon which the hydroxide ion further attacks both phenyl carbon-1 and the sulfur atom of the sulfone group to form the final products. The 14C tracer experiment indicates that the preference of the nucleophilic-attacking site of the hydroxide ion appears to vary with the reaction temperature. A similar alkaline fusion of 2-bromo-4-tolyl phenyl sulfone gave not only benzene, bromotoluene, and phenol, but also o- and m-cresol, indicating that the reaction proceeds through a somewhat different path. Meanwhile, the alkaline fusion of 2-chlorobenzenesulfinic acid appears to proceed through the o-sulfinic benzyne formation; thus 2-bromo-4-tolylsulfinic acid gave equal amounts of o- and m-cresols.
  • Akihiko Shimizu, Takayuki Otsu, Minoru Imoto
    1968 Volume 41 Issue 4 Pages 953-959
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    In order to clarify the relationship between the isomerization and polymerization of α- and β-olefins by various types of catalysts, the isomerizations of allylbenzene and propenylbenzene during their polymerizations were studied. In the presence of cationic catalysts (AlBr3, BF3O(C2H5)2, etc), neither the polymerization nor the isomerization of allylbenzene was observed, but propenylbenzene was found to be polymerized without the isomerization of the monomer to give a solid polymer which consisted substantially of a 1,2-structure, plus a minor unit of an isomerized structure. In the cases of the Natta catalysts [TiCl3-Al(C2H5)3, Al/Ti≥2], allylbenzene could easily be polymerized to a high-molecular-weight polymer with a 1,2-structure. During this polymerization, both positional and geometrical isomerizations of the unreacted monomer were observed, indicating that the propenylbenzene obtained from the isomerization did not participate in the polymerization of allylbenzene. It was also found that the polymerization and the positional isomerization of propenylbenzene by these catalysts did not occur.
  • Takayuki Naito, Susumu Nakagawa, Jun Okumura, Kiyoshi Takahashi, Ken-i ...
    1968 Volume 41 Issue 4 Pages 959-964
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    New compounds, 4-hydroxyisothiazoles, have been prepared by the reaction of α-amino ketones with thionyl chloride or sulfur monochloride, which is a novel procedure for cyclization to an isothiazole ring. Polar solvents, especially dimethylformamide (DMF), were preferable for this cyclization. The reaction hardly proceeded in a nonpolar solvent such as benzene, but was accelerated by an addition of a small amount of DMF.
  • Takayuki Naito, Susumu Nakagawa, Jun Okumura, Kiyoshi Takahashi, Kenji ...
    1968 Volume 41 Issue 4 Pages 965-971
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    4-Cyanoisothiazoles have been prepared by a novel procedure which comprises the reacreaction of β-cyano enamines with thionyl chloride or sulfur monochloride. The reaction proceeds favorably in nonpolar solvents or in the absence of solvent. However, the cyclization did not occur in dimethylformamide and instead an amidine derivative was isolated. The preparations of the corresponding isothiazole-4-carboxylic acids are also described briefly.
  • Noboru Sugiyama, Taketoshi Gasha, Hiroshi Kataoka, Choji Kashima
    1968 Volume 41 Issue 4 Pages 971-973
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The Structures and properties of α,β-unsaturated γ-oxo acid, acetyl- and benzoylacrylic acid, and their esters are studied.
  • Takeo Kaneko, Ikuko Takeuchi, Toshishige Inui
    1968 Volume 41 Issue 4 Pages 974-979
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The treatment of N-benzyloxycarbonyl-L-alanyl-L-serine methyl ester (I) with phosgene afforded the corresponding O-chlorocarbonyl derivative (II), which was then cyclized to methyl L-3-(N-benzyloxycarbonyl-L-alanyl)-2-oxo-oxazolidine-4-carboxylate (III) accompanied with N-benzyloxycarbonyl-L-alanyl-3-chloro-L-alanine methyl ester (IV) by refluxing in xylene. By the mild alkaline hydrolysis of III, N-benzyloxycarbonyl-L-alanine and L-2-oxo-oxazolidine-4-carboxylic acid (V) were isolated as a result of the selective cleavage of the peptide bond in which an amino group of the serine residue participated. This method was also applied to three other serine peptides; the same results were obtained.
  • Shoshichi Oguchi
    1968 Volume 41 Issue 4 Pages 980-987
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The solubility, ionization constant, and chelating behavior of dihydroxyquinoxaline,. mainly 5,8-dihydroxyquinoxaline (5,8-DHQ) derivatives, have been measured and will be discussed. The introduction of a hydroxyl group into quinoxaline greatly lowers the solubility. The order of the decreasing solubility of 2,3-disubstituted 5,8-DHQ in water (at 20°C) is: O(CH2)2OC2H5<H<OH<CH3<C6H5<OC2H5<Cl<SH<SC2H5. For 5,8-DHQ the introduction of electron-repelling groups into 2,3-positions raises both the pKNH and pKoH values, while the introduction of electron-attracting groups into the same positions lowers both pKNHand pKoH. 5,8-DHQ, and its derivatives form colored precipitates with metal ions, but some derivatives which have pKNH values lower than zero fail to show any precipitation or coloration. 6,7-DHQ forms precipitate, and the precipitation colors distinctively with Cr(III) or Fe(II). The composition and stability constant (K) of copper(II) chelates of 5,8-DHQ and its derivatives in a dioxane-water (10 : 90 v/v) solution were studied spectrometrically. The copper chelate of 5,8-DHQ had a metal: ligand ratio of 1 : 1 and a logK value of 6.28 at pH 4.0. The structures of these copper chelates will be proposed.
  • Yasuhiko Kondo, Yoshitoshi Honjo, Niichiro Tokura
    1968 Volume 41 Issue 4 Pages 987-992
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Three cases of combinations of the solvation free-energy differences in two solvents, with respect to a reactant and an activated complex, have been proposed. The theoretical expressions for the rate constant and for the activation energy in binary mixed solvents have been derived for each model. From the theoretical calculations based on these models, it has been demonstrated that the behavior of a system in which the reaction rates are mainly dependent on the difference in the solvation energies of an activated complex can be distinguished from behavior of a system where the reaction rates are controlled by the difference in the solvation energies of a reactant. The reaction rates of the Menschutkin reaction in binary mixed solvents containing liquid sulfur dioxide as one component of the mixed solvent have been analyzed on the basis of these models.
  • Yasuhiko Kondo, Miyoji Uchida, Niichiro Tokura
    1968 Volume 41 Issue 4 Pages 992-996
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The activation volume of the reaction of triethylamine with ethyl iodide has been measured in four solvents. A linear relationship has been observed between the values of ΔV0\ eweq for the Menschutkin reaction in various solvents and the products of the compressibility and the molar volume of the pure solvent, as has been suggested in a previous paper. From the slope of the plots of (−ΔV0\ eweq) vs. KV°, the product of the solvation number and the average pressure within the solvation shell of an activated complex has been calculated to be 2.6×103 (kg·cm−2) according to a model proposed by the authors. An abnormal acceleration due to pressure has been observed for the reaction of triethylamine with ethyl iodide in p-xylene and dioxane at 30°C. This acceleration effects has been attributed to the partial freezing of the solvent under high pressure.
  • Yoshiaki Furuya, Atsushi Morita, Iwao Urasaki
    1968 Volume 41 Issue 4 Pages 997-1000
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Bromobenzene is obtained in a 64% yield when an aqueous acetic acid solution containing a catalytic amount of sulfuric acid is slowly added to an aqueous acetic acid solution of benzene and potassium bromate at 60°C. It seems, according to the synthetic data, that the formation of bromobenzene is accelerated by an electron-releasing group. The rate of the consumption of active oxygen has been expressed as follows:
    v=k_2[BrO_3^-][C_6H_6]+k_3[BrO_3^-][C_6H_6]^2
    Here, both k2 and k3 gave a straight line against −log(CBH+CB), with a slope of ca. −2. The reaction is accelerated by sulfuric acid and does not occur at all in the absence of the acid. The evolution of oxygen gas was not observed during the reaction, but the presence of peroxyacetic acid and/or acetyl peroxide in the reaction mixture was indicated by paper chromatography. A mechanism which involves the rate-determining attack of protonated hypobromous acid and/ or protonated acetyl hypobromite on benzene has been suggested.
  • Koshin Miyazaki
    1968 Volume 41 Issue 4 Pages 1001-1005
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The various mixed dithiocarbamic-imidic anhydrides with the formula R2N–C(=S)–S–C-(=N–Ph)–Ph (I) rearranged to thiobenzoyl-thioureas with the formula R2N–C(=S)–N(–Ph)–C(=S)–Ph (II) when kept at an elevated temperature in an inert solvent. This rearrangement was found to be reversible, and it followed first-order kinetics. The value of the forward rate constant (k1) in o-dichlorobenzene at 100°C increased in the order: R=CH3>C2H5>n-C3H7>n-C4H9, and a good correlation between log k1 and σ* for R was obtained. The rearrangement following mixture of (CH3)2N–C(=S)–S–C(=N–Ph)–Ph and (C2H5)2N–C(=S)–S–C(=N–C6H5Cl-p)–Ph gave no crossed products. A probable reaction mechanism was proposed.
  • Takeo Saegusa, Shimpei Tomita, Takashi Ueshima
    1968 Volume 41 Issue 4 Pages 1005-1007
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    In the reaction of diazomethane with four aluminum haloalkoxides, Al(OCH2CF3)3 (I), Al(OCH2CCl3)3 (II), Al(OCH2CBr3)3 (III), and Al[OCH(CH2Cl)2]3 (IV), a methylene insertion into the aluminum-alkoxyl linkage was observed along with the polymethylene formation. By the methylene insertion, an organoaluminum compound with a haloalkoxymethyl-aluminum linkage is formed. Among aluminum alkoxides, these four haloalkoxides are distinguished by this methylene insertion. The usual aluminum alkoxides of unsubstituted alcohols do not undergo a methylene insertion reaction, but only the polymethylene formation. The difference in the reactivity towards diazomethane between the four haloalkoxides and usual alkoxides has been explained by the difference in acid strength.
  • Yojiro Tsuzuki, Motoo Koyama, Koko Tanabe
    1968 Volume 41 Issue 4 Pages 1008-1013
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Anomalous optical rotation has been observed not only with the ortho-nitrobenzylidene derivative of diethyl d-tartrate (Tsuzuki, Bull. Chem. Soc. Japan, 14, 35 (1939); Sci. Pap. I. P. C. Res. (Tokyo), 35, 425, 466 (1939)), but also with some acetylated ortho-nitrophenyl glycosides of the β-type (Capon et al., J. Chem. Soc., 1961, 5172; Montgomery et al., J. Am. Chem. Soc, 64. 690 (1942); Snyder et al., ibid., 75, 1758 (1953); Tsuzuki et al., Bull. Chem. Soc. Japan, 40, 1208 (1967)). To investigate this anomalous effect of the ortho-nitro group the authors have made rotatory dispersion studies on several derivatives of diethyl d-tartrate as well as its alkylidene derivatives. Of these compounds examined, the compound (I) with a nitro group in the ortho-position of the phenyl group shows a positive Cotton effect at about 340 mμ, and it has been found that the nitrophenyl group is optically active. Furthermore, in order to inquire into this anomaly the authors have observed the CD, UV and NMR spectra of these compounds, from which it is concluded that the conformations of the acetal rings of all the compounds are nearly equal, and the anomalous dispersion of the compound I at about 340 mμ, is assumed to be due to the n→π* transition of the nitro group with a slight shoulder appearing at 325 to 350 mμ. In view of these facts it is considered that the ortho-nitro group is twisted from the plane of the benzene ring caused by the steric hindrance of the bulky acetal ring.
  • Tetsuo Suami, Frieder W. Lichtenthaler, Seiichiro Ogawa, Yasuo Nakashi ...
    1968 Volume 41 Issue 4 Pages 1014-1017
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Bromination of myo-inosadiamine-l,3 dihydrochloride or its di-N-acetyl derivative with acetyl bromide and acetic anhydride yielded pentaacetyl-2-bromo-2-deoxy-scyllo-inosadiamine-1,3 (III), which upon reductive debromination afforded pentaacetyl-2-deoxystreptamine (IV). The configurations of the new compounds obtained were established by nuclear magnetic resonance and chemical evidences. A mechanism of the bromination reaction is presented, based on the configuration of the bromo-compound.
  • Junji Aoki
    1968 Volume 41 Issue 4 Pages 1017-1020
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    By reducing flavanthrone (II), 8,16-diazapyranthrene (V) (denoted as flavanthrene) was obtained. On the other hand, leucoflavanthrone dibenzoate was also prepared. Since these two substanses give nearly identical absorption spectra, the leucobenzoate is considered to have the VI formula (5,13-dibenzoyloxy-8,16-diazapyranthrene) and to belong to the same conjugated system as flavanthrene. Consequently, it may be considered that the leuco-form of flavanthrone corresponds to the IV formula (5,13-dihydroxy-8,16-diazapyranthrene) in which two carbonyl groups are reduced, but not the III formula (8-hydro-13-hydroxy-5-oxo-8,16-diazapyranthrene) previously presented. In addition, the leucobenzoate can also be synthesized by boiling the quinone with zinc dust and benzoyl chloride in o-dichlorobenzene containing pyridine. This method, devised by the author, is easy to perform and gives a good yield.
  • Yoshio Baba
    1968 Volume 41 Issue 4 Pages 1020-1021
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
  • Yoshio Baba
    1968 Volume 41 Issue 4 Pages 1022-1023
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
feedback
Top