Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 43 , Issue 9
Showing 1-50 articles out of 87 articles from the selected issue
  • Yuko Hasegawa
    1970 Volume 43 Issue 9 Pages 2665-2670
    Published: 1970
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The stabilities of the indium(III) complexes in 4 M sodium perchlorate solutions with eight univalent anionic ligands have been studied at 25°C by using a TTA-chelate extraction method and a TBP adduct extraction method. The following conclusions have been reached. The stabilities of the indium(III) halide complexes are larger in this order; Cl>Br>I; on the other hand, those of indium(III) complexes with the halate anions increase in the order: ClO3<BrO3<IO3. The former forms more stable complexes than the latter. Thiocyanate ions form the most stable indium(III) complexes (the first to the fifth complexes), while nitrate ions form the least stable one (only the first complex). The values obtained by the TTA method are almost identical with those obtained by the TBP method. It was also concluded that although the TTA method could be applied to all the systems studied, it is more suitable for the examination of the lower complexes; the TBP method, on the other hand, could be used only for the systems in which an extractable third complex is formed, but it could give more accurate constants for the higher complexes. Thus, only a combination of these two methods can give all the equilibria in a system where many complexes are formed.
  • Koichiro Nakanishi, Hidekazu Touhara, Nobuatsu Watanabe
    1970 Volume 43 Issue 9 Pages 2671-2676
    Published: 1970
    Released: March 27, 2006
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    The heat of mixing has been measured at 25.00°C and 45.00°C for binary mixtures of methanol with n-butylamine, diethylamine and triethylamine. A twin-type conduction calorimeter was used. All the systems exhibit large negative enthalpies of mixing, which become slightly less negative as the temperature increases. From the present results and vapor-liquid equilibrium data, the excess free energy and entropy of mixing at 25.00°C have been calculated for each system. The sign and magnitude of the excess functions were as follows: HM<TSE<GE<0 for methanol with n-butylamine and diethylamine, GE>0, TSE<HM<0 for methanol with triethylamine. These facts were interpreted in terms of steric effects and specific solvation in the hydrogen bonding between hydroxyl group and amino bases.
  • Yoshio Toshiyasu, Ko Kimura, Ryoichi Fujishiro
    1970 Volume 43 Issue 9 Pages 2676-2679
    Published: 1970
    Released: March 27, 2006
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    The electric dipole moments of α,ω-alkanediols such as HO–(CH2)n–OH (n being varied from 2 to 5) were measured both in dioxane and in a mixed solvent of dioxane with carbon tetrachloride at 25°C. The observed dipole moments increase with the increasing n until n=4, and then decrease for n=5, while the calculated dipole moments based on the vector addition of group moments on the assumption of the random coil model for alkane chains increase monotonously as n increases from 2 to 5. It is concluded that for both propanediol and butanediol the conformations forming the intramolecular hydrogen-bond which have the larger dipole moments contribute appreciably to the observed dipole moments. The dipole moment of pentanediol is close to the calculated one for the random coil model, whereas that of ethylene glycol suggests the existence of the intramolecular hydrogen-bond. Population analysis of the hydrogen-bonded species in solutions is also given.
  • Tsutomu Seimiya
    1970 Volume 43 Issue 9 Pages 2680-2689
    Published: 1970
    Released: March 27, 2006
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    The adsorption of tritium-labelled sodium stearate at the air/water interface was directly measured radiometrically using an ultra-thin-windowed Geiger-Müller tube for varying soap concentrations, pH values, and temperatures. The changes in the amount of adsorption and in the surface tension were simultaneously traced with the lapse of time. The pressure-area curve was then obtained by the successive plotting of the surface pressure against the area at the same aging; the curve at equilibrium was also obtained. Thus, the pressure-area relationship of the adsorbed monolayer was automatically measured during the course of adsorption approaching equilibrium. A close resemblance was observed between the monolayer of stearic acid on-neutral water and the adsorbed films on the stearate solution of pH values from 8.85 to 9.30 at 30°C. The amount of adsorption measured for an alkaline solution often exceeds the value to be expected from the saturation value for a completely-ionized stearate monolayer. The pressure-area characteristics suggested a transition from the condensed state of the adsorbed film at a higher surface concentration to an expanded state at a lower concentration. It was also confirmed, by measuring the amount of adsorption in the atmospheres of both nitrogen and air containing carbon dioxide, that the atmospheric carbon dioxide acts to increase the adsorption of stearic acid on the aqueous surface. The diffusion coefficient of the adsorbing solute, calculated from the initial rate of adsorption, showed a smaller value than that obtained by conductometric measurements.
  • Masakatsu Kochi, Yoshiya Harada, Tomohiko Hirooka, Hiroo Inokuchi
    1970 Volume 43 Issue 9 Pages 2690-2702
    Published: 1970
    Released: March 27, 2006
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    The quantum yield and the energy distribution of photoelectrons were measured for organic crystals in the vacuum ultraviolet region. A model was presented for the photoemission from organic crystals with a narrow valence band, and a semiempirical power law was derived for the yield near the threshold. The ionization potentials found from the spectral distribution of the quantum yield using this model were as follows: anthracene–5.68 eV, naphthacene—5.43, pentacene—5.04, perylene—5.33, indanthrone—5.17, and tetrathionaphthacene—4.42. The effect of electrons which escape after one inelastic scattering was observed. It was shown how the contribution of once-scattered electrons can be separated in the energy distribution. The threshold for “pair production” was estimated to be nearly equal to the band gap for perylene and a little higher than the band gap for quaterrylene. The fine structures observed both in the yield spectra and in the energy distribution can be accounted for by assuming the existence of additional valence bands.
  • Hiroko Yamabe, Hiroshi Kato, Teijiro Yonezawa
    1970 Volume 43 Issue 9 Pages 2702-2705
    Published: 1970
    Released: March 27, 2006
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    The electronic structures of several pseudo acids are studied, in connection with their reactivity and stability, by the Extended Hückel method. The linear relationship between the observed pKa value and the change in the calculated electronic energy, ΔE, in the course of the dissociation of the pseudo acids is also observed. The order of the stability of the carbanion, referred to its parent acid, as estimated from our calculations, is; CH2NO2>CH2COCH3>CH2CN. Di- or tri- substituted carbanions should be more stable. This order is parallel with that of the electron-attracting abilities of the groups adjacent to the methylene group. The highest-occupied MO of the carbanion is remarkably unstable, resembling a lone-pair level, and the atomic orbital population of that MO is large at the Pz AO of the carbon. This reflects the high reactivities of the carbanion as a reaction intermediate; the electrophilic addition probably takes place at the carbon atom.
  • Hiroshi Kawabe, Masaya Yanagita
    1970 Volume 43 Issue 9 Pages 2706-2713
    Published: 1970
    Released: March 27, 2006
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    The two parameters in the modified Henderson-Hasselbach equation, pH=pKan′log-[(1−α)⁄α], where pKa and n′ are empirical constants and where α is a degree of the ionization of a polymeric acid, were evaluated on the assumption that the ionization of polyelectrolytes is electrostatically affected in the main by a few neighboring ionized groups and that the over-all ionization is composed of only a few elementary ionization. The titration curves of various polyelectrolytes in the absence of salt could be classified into two types: ΔpK′≥2 and ΔpK′<2, where ΔpK′ is the difference between the succeeding ionization constants. The maleic acid-styrene copolymer and polyvinyl amine belong to the former type, while polyacrylic acid and pectinic acid belong to the latter. In the former, a plot of pH against log[(1−α)⁄α] nearly falls on a line in only a limited range and n′ is substantially equal to the number of elementary ionizations. In the latter, both pKa and n′ are related to the distance between the groups. The titration curve of polyacrylic acid, drawn by means of the above equation with the parameters calculated on the basis of the kinetic data of the alkaline hydrolysis of polymethyl acrylate, was in good agreement with the observed titration curve. The titration data of other polyelectrolytes also fall nearly on their calculated titration curves.
  • Hideo Yamazaki, Kyoji Shinsaka
    1970 Volume 43 Issue 9 Pages 2713-2718
    Published: 1970
    Released: March 27, 2006
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    The electron-scavenging process by a scavenger and the random recombination between ions and electrons in a spur in the radiolysis of nonpolar hydrocarbons have been investigated theoretically on the basis of the extended type of Smoluchowski equation. To obtain the approximate solutions, a model of the distribution of charged species in which a positive ion core is surrounded by electrons is assumed; several approximations are also made during the calculation. The reaction rate of the electron scavenging is expressed by the overlapping integral between the concentration of the electrons and that of the scavenger. The rate of the recombination reaction is approximately expressed as the total flux of the electrons flowing into the core of parent ions. The G value of electron scavenging shows a Langmuir-type dependence on the concentration of the electron scavenger. The values of the slope of the sigmoidal curve at the mid point and of the corresponding scavenger concentration almost agree with the experimental value.
  • Otohiko Nomoto, Harumi Endo
    1970 Volume 43 Issue 9 Pages 2718-2723
    Published: 1970
    Released: March 27, 2006
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    An acoustic interferometer is employed to obtain the variation of sound velocity with concentration and temperature in hexamethylenetetramine (HMT), urea, thiourea, acetamide and N,N-dimethylformamide (DMF) and their aqueous solutions. The plot of velocity of aqueous solutions of these organic substances against temperature gives parabolic curves similar to one for pure water. In these curves, the maximum height of sound velocity is higher than that for pure water and the temperature at maximum point is lower than for water. The curves of sound velocity vs. concentration at various temperatures show values of maximum velocity at intermediate concentrations. The maximum value decreases with increasing temperature and finally disappears in some cases. Results show that the velocity dependency on temperature and concentration are qualitatively determined by the relative concentration of non-associated water to cluster. The sound velocity of acetamide and DMF is 1404.4 m/sec (65°C) and 1478.8 m/sec (20°C), respectively, and shows negative temperature coefficients of −2.68 m/sec/deg and −3.90 m/sec/deg, respectively.
  • Hisashi Ueda, Naoyuki Todo
    1970 Volume 43 Issue 9 Pages 2723-2726
    Published: 1970
    Released: March 27, 2006
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    The effect of several additives on the ESR of copper oxide was studied. Among the additives studied, amines and NH3 had peculiar effects on the ESR spectra. From the spectrum formed by NH3 it is concluded that the (Cu–NH3)2+ complex cation is formed on the surface of a CuO particle. The formation of this complex cation obeyed a pseudo-flrst-order rate and can be interpreted in terms of the surface reaction between the exposed Cu2+ and NH3. Among the amines studied, only primary amines gave ESR spectra which provide evidence for the existence of (Cu-amine)2+complex cations. The foregoing fact and the results obtained on the three isomers of chloroaniline indicate that a strong s-character of the lone-pair orbital is needed if an amine molecule is to occupy a surface defect of the O2−, by which the Cu2+ is exposed on the surface, thus forming a complex cation. By these facts, the d-orbital of Cu2+, which can overlap with the nitrogen lone pair of the amine molecule, is concluded to be dz2. The three principal values of the g-tensor for the (Cu–NH3)2+complex cation depend greatly on the temperature, indicating that this cation has some rotational and vibrational motions below 130°C, at which point Cu2+ and NH3 dissociate.
  • Morio Setaka, Takao Kwan
    1970 Volume 43 Issue 9 Pages 2727-2731
    Published: 1970
    Released: March 27, 2006
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    ESR spectra of adsorbed oxygen species were investigated on cadmium, cerium and uranium oxides supported on alumina. The principal g values, gx, gy and gz of the oxygen species were computed and compared with those on the other metal oxides. It was pointed out that the principal g values observed on cerium and uranium oxides are interpretable by a peroxy-like model rather than an O2 radical. ESR spectra due to radicals formed on mixing solutions of VO2+ or UO22+ (containing Ti3+) with H2O2 were also investigated by a rapid-mixing flow technique. The g value of the radicals was very close to the isotropic one of the peroxy-like species adsorbed on the corresponding metal oxide. The electronic nature of the interaction of oxygen species with metal ions at surface and with those in solution was comparatively discussed.
  • Koichi Kikuchi, Hiroshi Kokubun, Masao Koizumi
    1970 Volume 43 Issue 9 Pages 2732-2739
    Published: 1970
    Released: March 27, 2006
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    Choosing eosin and erythrosin as donor and anthracene and 9-methylanthracene as acceptor, we have kinetically investigated the triplet energy transfer process by flash technique involving emission measurement. In these systems the differences of T-levels of donor and acceptor are of the order of kT at most, and it was anticipated that a reversible energy transfer would occur. It has been established that it actually occurs in eosin-anthracene and erythrosin-anthracene, and very likely occurs in erythrosin-9-methylanthracene. Furthermore, it has been found that in the first two systems the energy transfer rate for the process, donor→acceptor is about half that for the process, acceptor→ donor. This means that the rate in the present systems is determined by some other factor than the triplet level. Discussions have been given on the model for energy transfer.
  • Shoji Shida, Masao Tsukada
    1970 Volume 43 Issue 9 Pages 2740-2745
    Published: 1970
    Released: March 27, 2006
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    The mercury-photosensitized reaction of acetylene has been studied with equimolar mixtures of C2H2 and C2D2 under various conditions of pressure, temperature, and additives. It is shown that the distribution of isotopically substituted benzenes can be explained by a modified excited state mechanism equally as well as, or more favourably than by the free radical mechanism. The results on deuterium-acetylene mixtures photosensitized by Hg(3P1), however, suggest that benzene is also formed by the reaction of hydrogen atoms and acetylene molecules. The rates of benzene formation and of the polymer formation increased gradually with pressure in low pressure region to attain a maximum and then decreased. Argon very strongly inhibited the benzene formation and, to a less extent, the polymer formation. The primary process is explained by assuming the formation of a transient complex of a triplet mercury atom and an acetylene molecule.
  • Masashi Imamura, Masao Matsui, Takashi Karasawa
    1970 Volume 43 Issue 9 Pages 2745-2749
    Published: 1970
    Released: March 27, 2006
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    The yield of ferric ions in the radiolysis of an aqueous ferrous ammonium sulfate solution has been determined in the very high LET (linear energy transfer) range. The radiations used were ions of carbon-12 and nitrogen-14, which were accelerated by means of the IPCR cyclotron and which had energies (Es) of 31–77 MeV for C-ions and of 17–78 MeV for N-ions; the LET ranges for water were 24–46 eV/Å and 26–85 eV/Å respectively. From the plot of G(Fe3+)Es vs. Es, the value for G(Fe3+) at an infinite LET was found to be in the vicinity of 2.9. It has also been shown that there is a substantial difference in the instantaneous yield (Gi) between the two ion radiations of the same LET; this may be ascribed to the differences in the track structures of the heavy-ion radiations.
  • Tadashi Okada, Hiroo Oohari, Noboru Mataga
    1970 Volume 43 Issue 9 Pages 2750-2758
    Published: 1970
    Released: March 27, 2006
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    Mechanisms of the intermolecular electron transfer process in the electronically excited states of solute molecules have been studied in relation to the fluorescence quenching reactions in solution, employing pyrene as a fluorescer and some aromatic amine and cyano compounds as quenchers. The quenchers showed various strengths of the quenching actions which were classified and discussed on the basis of a new theoretical model of electron transfer process in excited state. Tetracyanoethylene showed a quite strong quenching action which was interpreted in terms of a long range electron transfer from excited pyrene to tetracyanoethylene. The relation between the exciplex formation, the electron transfer reaction due to the short range interaction and that due to the long range interaction have been discussed.
  • Shuichi Iida, Rei Yugeta, Shin Sato
    1970 Volume 43 Issue 9 Pages 2758-2761
    Published: 1970
    Released: March 27, 2006
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    The formation of methane and hydrogen in the γ-radiolysis of neopentane and isooctane has been studied in the presence of an electron scavenger (N2O) and/or a radical scavenger (styrene). The G-value of nitrogen from neopentane solutions of nitrous oxide was found to be about twice the sum of the decrease in the G-values of methane and hydrogen. From isooctane solutions, G(N2) was more than three times the sum of the decrease in G(H2) and G(CH4). This can be interpreted on the assumption that a significant part of the neutralization of isooctane ions with electrons induces the fragmentation into C4-hydrocarbons. It was also found that a part of the methane formed (0.9 G in neopentane and 0.2 G in isooctane) was not produced by the reactions of ions or methyl radicals, but by a “molecular” process, probably the decomposition of the highly-excited states.
  • Seiichi Kurihara, Kazuo Fueki, Takashi Mukaibo, Yasuo Wada
    1970 Volume 43 Issue 9 Pages 2761-2766
    Published: 1970
    Released: March 27, 2006
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    The redox reaction between thin wüstite foil and CO2 or CO was studied by means of a microbalance in a temperature range 900–1075°C. It was found that the reaction at the gas-wüstite interface is rate-controlling and that the reaction rate is expressed as
    V_ox=k_OP_CO2a_O^-m/3 and V_red=k_O’P_COa_O^n/3
    where aO is the oxygen activity of wüstite, and m and n are 2.1–2.2 and 0.8–1.2, respectively. On the basis of the theory by Kobayashi and Wagner, the most predominant mechanism is concluded to be
    CO_2+2\ominus\ ightleftarrowsCO+O^2-
    Actigation energies for kO and kO′ were 35+3 and 32+3 kcal/mol, respectively.
  • Satoshi Takao, Shoji Shida
    1970 Volume 43 Issue 9 Pages 2766-2771
    Published: 1970
    Released: March 27, 2006
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    The effect of electron scavenger (SF6) on the radiolysis products of N2O was examined. The sensitization of N2O by various rare gases was also measured. In the presence of an electron scavenger we got 3.0 for the value of −ΔG(−N2O) in good agreement with the value of G(e) for N2O. In the experiments of Xe or Kr containing small amounts of N2O, the G(−N2O) values were nearly equal to the respective G(e) values for the rare gases, and the addition of SF6to the Xe-N2O system almost completely inhibited nitrogen formation. The results show that one electron decomposes just one molecule of N2O. This fact can not be accounted for by the hitherto assumed mechanism, and a new mechanism involving N2O is proposed for ionic processes in the radiolysis of N2O. In the N2O-rare gas mixtures of various compositions, the sensitized yields of N2O decomposition per 100 eV energy absorbed by rare gases were divided into two groups, e.g., the yields from He, Ne mixtures were about twice as large as those from Ar, Kr and Xe mixtures. This result is discussed in terms of charge transfer and the Penning ionization.
  • Yôichi Iida
    1970 Volume 43 Issue 9 Pages 2772-2776
    Published: 1970
    Released: March 27, 2006
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    The anion-radical salts derived from p-chloranil, 2,5-dibromo-3,6-dichloro-1,4-benzoquinone, and p-bromanil were prepared. The absorption spectra in an acetone solution and the diffuse reflection spectra of the solid salts were examined. These solid salts were then classified into three groups, namely, those showing the spectrum of the anion-radical monomer, those showing a strong charge-transfer band characteristic of the solid salts, and, finally, those showing not only the spectrum of the anion-radical monomer but also an intermolecular charge-transfer band. The mode of intermolecular interaction in these anion-radical salts was discussed according to this classification. Their magnetic behaviour was also speculated upon on the basis of the charge-transfer interaction.
  • Mitsutoshi Tanimoto, Kozo Kuchitsu, Yonezo Morino
    1970 Volume 43 Issue 9 Pages 2776-2785
    Published: 1970
    Released: March 27, 2006
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    The molecular structure of carbon suboxide, C3O2, has been studied by the sector-micro-photometer method of gas electron diffraction. The C=O and C=C distances (rg) have been determined to be 1.1632±0.0013 Å and 1.2894±0.0022 Å, respectively, where the uncertainties represent estimated limits of error. The observed mean amplitudes for three nonbonded atom pairs and their shrinkages are found to be much larger than those expected for ordinary molecules, with linear framework. A usual harmonic approximation up to the quadratic terms of displacements cannot account for the observed values in this molecule. This indicates that the πu bending vibration ν7 has a very low frequency (an effective frequency being about 68 cm−1) and that this vibration is essentially a bending motion of the valence angle of the central carbon atom, in agreement with recent spectroscopic studies. The effect of the large-amplitude vibration on mean amplitudes and shrinkages has been studied in detail by using a model, which assumes that atomic motions take curvilinear paths in the ν7 vibration with the valley in the potential surface running along the loci of fixed bond lengths. The potential function for this bending motion has been estimated by a least-squares analysis on the observed structural parameters. The potential function is given by V(Q7)=(23±5)Q74−(100±31)Q72 (cm−1), where the uncertainties representing random standard errors take the upper and lower signs in the same order and Q7= sin α⁄0.145 (amu1⁄2 Å). The potential rises steeply with increasing angle of bending, α=1⁄2[180°∠–(C=C=C)], and appears to have a small hump at α=0. This “quasi-linear” potential function is consistent with the recent experimental estimates by Seip et al. within experimental errors, but the double-minimum nature of the potential is subject to a further critical examination by other experimental methods.
  • Teiki Iwaoka, Shigeya Niizuma, Masao Koizumi
    1970 Volume 43 Issue 9 Pages 2786-2795
    Published: 1970
    Released: March 27, 2006
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    By the combined use of the steady-light experiment and a flash technique, photoreduction of phenazine in methanol, ethanol, isopropanol and by EDTA in the aqueous solution and also the related elementary processes have been studied. The photoproduct has been identified as dihydrophenazine of which the absorption spectrum has been measured for the first time. It has been concluded that the lowest triplet, T(π–π*) is not a reactive state. Most probably the reactive state is a higher T(n−π*). The quantum yields of photoreduction in methanol, ethanol, and isopropanol are respectively 0.023, 0.037 and 0.050. Singlet-Triplet transition probability (ΦST) has been found to be >0.33 in the aqueous solution. Semiquinone produced in alcohols disappears by disproportionation reaction with almost the diffusion controlled rate constant while in the aqueous solution the disproportionation is much slower and at high EDTA concentrations, semiquinone is further reduced by EDTA. The absorption due to a molecular compound consisting of phenazine and dihydrophenazine has been detected in the visible region. It has been suggested that a certain equilibrium exists between three compounds and that a rather stable radical species, the existence of which has been proved by an ESR spectroscopy, participates in this equilibrium.
  • Mikio Hoshino, Hiroshi Kokubun, Masao Koizumi
    1970 Volume 43 Issue 9 Pages 2796-2800
    Published: 1970
    Released: March 27, 2006
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    It has been found that the aqueous solution of N-nitroso-N-methylaniline when irradiated by 253.7 nm shows photochromism. The unstable photoproduct reconverts to the original compound photochemically as well as thermally. The quantum yields for the forward and backward reaction are respectively 0.23 and 0.58. N-Nitroso-N-ethylaniline also reacts in the similar way. In the alcoholic solutions, different types of reaction occurred; in the absence of oxygen the reaction is mainly the formation of N-methylaniline. It has been suggested that the present photochromism is due to the cis-trans isomerization.
  • Takayoshi Yoshimori, Ikuko Matsubara
    1970 Volume 43 Issue 9 Pages 2800-2804
    Published: 1970
    Released: March 27, 2006
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    The sensitive amperometric end-point procedure (Anal. Chem., 23, 1662 (1951)) with an antimony electrode is used in the titrations of acids. The cyclic voltammetric curves of the electrode indicate the possibility of the use of the above method for the titration of acids. The purities of potassium biphthalates (primary standard substances) are determined directly by precise coulometric titration with this end-point location. The standard deviations of the results (99.999%) are 0.007 or 0.008%. The purity of the benzoic acid prepared as the standard material for the calorimeter is also determined by this method. The standard deviation of these results (99.993%) is 0.009%.
  • Krishnaji, S. C Srivastava, Dina Nath
    1970 Volume 43 Issue 9 Pages 2805-2807
    Published: 1970
    Released: March 27, 2006
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    Dielectric relaxation times and distribution parameters of three esters in benzene solutions have been evaluated using three methods, viz., Cole-Cole arc plot method, Higasi’s single frequency method and the Gopal Krishna method. Three microwave frequencies have been used to determine a′ and a″ apart from the static and optical frequencies for a0 a. The distribution parameters obtained from Cole-Cole arc plot and Higasi’s method are in good agreement showing that the sploes a′ and a″ have been determined accurately. In these esters the values of the distribution parameter are high. Since the dipole-dipole interactions are negligible in dilute solutions, the higher values of the distribution parameter suggests the existence of multiple relaxation processes.
  • S. N. Bhattacharyya, D. K. Bardhan
    1970 Volume 43 Issue 9 Pages 2808-2811
    Published: 1970
    Released: March 27, 2006
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    Aqueous solutions of potassium periodate in neutral medium were irradiated with X-rays and with Gobalt-60 gamma rays. It was observed that the periodate on radiolysis is reduced only to iodate and no other reduction product was detected. A mechanism for the radiation induced reduction of periodate in aqueous solution is proposed and discussed. Effect of methanol on the course of radiolysis has also been studied.
  • Masahiro Tsubouchi
    1970 Volume 43 Issue 9 Pages 2812-2815
    Published: 1970
    Released: March 27, 2006
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    A new rapid, sensitive and selective method is proposed for the spectrophotometric determination of a trace of mercury (II) by solvent extraction. The method is based on the formation of an ion-pair complex between the tribromo-mercury(II) complex anion and the dyestuff cation obtained by oxidation of variamine blue B. The optimum pH range for the color reaction is 2.5–4. The blue complex can be extracted into nitrobenzene and has a maximum absorption at 605 mμ in the organic solvent. Beer’s law holds in the range 3.2×10−6−2.2×10−5 M of mercury(II) in the aqueous layer before the extraction, with a molar absorptivity of 4.03×104 mol−1cm−1 l at 605 mμ. The color reaction is instantaneous and the complex remains stable 15 mintes in the nitrobenzene layer. Of the 22 cations and 11 anions examined, tin(II), tin(IV), antimony (III), iodide, cyanide, and thiocyanate showed serious interferences.
  • Yuki Fujii
    1970 Volume 43 Issue 9 Pages 2815-2820
    Published: 1970
    Released: March 27, 2006
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    The following nickel (II) complexes containing ethylenediaminemonoacetate anion(s) (edma) were newly prepared from an aqueous solution containing nickel(II) ion and edma: [Ni(edma)(H2O)3]X (X=Cl and Br), [Ni(edma)I]4, and [Ni(edma)2]·2H2O. By the thermal decomposition of [Ni(edma)(H2O)3]X, [Ni (edma) X]4-type complexes (X=Cl and Br) were also prepared. By absorbing three molecules of water in an atmosphere, two new, mixed-complexes containing a halogen anion and water molecule(s), [Ni(edma)Cl(H2O)2]·H2O and [Ni(edma)Br(H2O)]2·4H2O (dimer), were prepared from [Ni(edma)X]4. By the measurements of the absorption spectra, the magnetic moments, and the dehydrations, their structures were all assigned to octahedral. The [Ni(edma)X]4 complexes (X=Cl, Br and I) were presumed to have the tetramer structure, where four halogen anions are triply bridged to the nickel(II) ion. The difference between the [Ni(edma)(H2O)3]X, [Ni(edma)Cl(H2O)2]·H2O, and [Ni(edma)Br(H2O)]2·4H2O complexes were clearly observed on the basis of their deri-vatographic behavior. The mechanisms of the dehydrations were also discussed.
  • Teisuke Murayama, Toshiko Sawaki, Shukichi Sakuraba
    1970 Volume 43 Issue 9 Pages 2820-2823
    Published: 1970
    Released: March 27, 2006
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    In the anodic process of thiosulfate at a dropping mercury electrode, the formation of a species Hg(S2O3)34− is considerable even in dilute solution. An equation of current-potential curve is derived with proper consideration for the formation of the species. The successive stability constant of Hg(S2O3)34− was calculated to be 3×102 (at 25°C and an ionic strength of 0.2) by comparing the equation with experimental results.
  • Hui-Tuh Tsai, Toyoaki Kato, Yoshinaga Oka
    1970 Volume 43 Issue 9 Pages 2823-2827
    Published: 1970
    Released: March 27, 2006
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    We have studied a method for the determination of rubidium by activation analysis with brems-strahlung photons, with strontium used as the internal-reference element. This method is based on the γ-ray spectrometric measurement of the 84Rb activities produced by the 85Rb(γ,n) reaction and on the comparisons of those activities with that of 83Rb arising from strontium as a result of the (γ,p) reaction. The yields of various photonuclear reactions in rubidium and in strontium have also been examined as a function of bremsstrahlung maximum energies up to 60 MeV, and the best conditions for the determination of rubidium are proposed. When the maximum energy was set at 18 to 20 MeV, no interfering reactions occurred; a rubidium content down to about 2 μg can be determined accurately. A comparison of solid-state and scintillation γ-ray spectrometry in this method has also been included with respect to the sensitivity and the selectivity.
  • Yoshihisa Matsui, Yoshio Date
    1970 Volume 43 Issue 9 Pages 2828-2835
    Published: 1970
    Released: March 27, 2006
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    The polarographic behavior of bromine and the tribromide ion at the dropping mercury electrode was investigated in dimethylformamide. A freshly-prepared solution of bromine gives two cathodic waves. When the solution is allowed to stand at 25°C in the dark, however, the first wave gradually becomes anodic, independently of the electrolysis. When the first wave is completely anodic, an equilibrium is established. The resulting polarogram coincides with that of hydrogen tribromide. The formation of hydrogen tribromide was ascribed to the chemical reduction of bromine by dimethylformamide. Diffuse sunlight accelerates the decomposition of bromine, which in turn yields hydrogen bromide. It was also suggested that, when the dropping mercury is used as an indicator electrode, bromine and the tribromide ion may react with the dropping mercury prior to being electrolyzed, forming mercuric bromide and the tribromomercurate ion respectively, which may in turn depolarize the indicator electrode.
  • Teikichi Sasaki, Takanobu Shiokawa
    1970 Volume 43 Issue 9 Pages 2835-2839
    Published: 1970
    Released: March 27, 2006
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    The transient annealing behavior of bromine recoils produced by isomeric transition was studied in five alkali metal bromates. In the case of 80mBr-labelled potassium bromate, the iso-thermal annealing curves were characterized by maximum and minimum points. A numerical treatment of them indicated that, at the earlier stage of the thermal treatment, the annealing processes proceeded very fast, which was ascribed to the characteristics of the isomeric transition recoils. A remarkable effect of the cationic components on the thermal annealing was observed and interpreted in terms of their ionization potentials.
  • Akira Ouchi, Toshio Takeuchi, Iwao Taminaga
    1970 Volume 43 Issue 9 Pages 2840-2844
    Published: 1970
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The benzothiazole, 2-amino-benzothiazole, benzimidazole-2-thiol, and benzothiazole-2-thiol adducts of tin(II, IV) chlorides, antimony(III) chloride, and antimony (III) bromide with the formulae of Mn+LmXn (where L is the ligand and where X is Cl or Br) were synthesized. From their electronic and infrared spectra, it can be seen that the 2-amino-benzothiazole adducts are more stable than those of other ligands and that the metal-ligand bonds in the former remain, even in the ethanolic solution.
  • Yayoi Ohashi, Toshio Takeuchi, Akira Ouchi, Yukichi Yoshino
    1970 Volume 43 Issue 9 Pages 2845-2850
    Published: 1970
    Released: March 27, 2006
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    The dihydrates and anhydrous copper(II) complexes with methyl, ethyl, n-propyl, isopropyl, n-butyl, and benzyl thioglycolic acids were synthesized, and their properties were investigated. The magnetic data show that the copper in the complexes is divalent and that the complexes do not have a copper(II) acetate structure. The spectroscopic data show that these ligands bond to the central metal ion as strongly as does amino acid or water. In the case of isopropyl thioglycolato copper(II) dihydrate, the blue and the violet isomers were obtained. The structures of the complexes in the solid state as well as in the solution were discussed.
  • Niro Matsuura, Tsin-ko Lin, Yoshimitsu Kobayashi
    1970 Volume 43 Issue 9 Pages 2850-2858
    Published: 1970
    Released: March 27, 2006
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    The ion-exchange chromatographic technique was used in order to find the average chain number of a polyphosphate product. For the assignment of the nth polymer in the obtained chromatogram, the dependence of the distribution coefficient, Kd, on the eluent concentration examined by the use of both 20-cm and 60-cm resin columns. A lower series of polyphosphate was included in a relatively large amount in order that the average chain number based on the chromatographic analysis could be duly appreciated only for the case of basic polymers with lower molecular weights. For a product “Graham Salt” with a number of phosphate links, the higher series of polyphosphate could not be desorbed entirely from the resin column; the accurate estimation of the average number was, then, improbable. The viscosity method is also not advisable to use the computation of a mean polymerization number in the polyphosphate with a low molecular weight. An attempt was made to improve the data on the average chain number by the viscosity measurements together with the chromatographic analysis of the polymer constituent.
  • Tatsuro Ouchi, Masayoshi Oiwa
    1970 Volume 43 Issue 9 Pages 2858-2862
    Published: 1970
    Released: March 27, 2006
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    Dimethallylidenepentaerythritol (DMAPE) and dicrotylidenepentaerythritol (DCPE) have been copolymerized with maleic anhydride (Manh), using benzoyl peroxide as an initiator. From the results of the UV spectrum concerning the rate of copolymerization, it was found that the copolymerization might proceed on the pseudo-terpolymerization of the charge transfer complex-allylidene group-Manh. The following functional group reactivity ratios were calculated at 60°C in these systems:
    & DMAPE(M_1)-Manh(M_2)
    & r_1cK=0.77, r_2cK=0.058
    & r_1=O.05, r_2=0.025
    & DCPE(M_1)-Manh(M_2)
    & r_1cK=0.89,  r_2CK=0.057
    & r_1=0.02, r_2=0.020
  • Tatsuro Ouchi, Yorihiro Imase, Masayoshi Oiwa
    1970 Volume 43 Issue 9 Pages 2863-2870
    Published: 1970
    Released: March 27, 2006
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    The polymerization of di-(β-methacrylyloxypropionaldehyde)-pentaerythritolacetal (Dβ-MPP) and the copolymerizations of DβMPP with styrene (St) and acrylonitrile (AN) have been carried out at 60°C, using benzoyl peroxide as an initiator. They have then been discussed kinetically from the point of view of cyclopolymerization. The results can be summarized as follows:
    1) The relation among the rate of polymerization, Rp, the initiator concentration, (I), and the monomer concentration, (M), can be expressed by the following equations;
    & R_p/(I)^1/2=A(I)^1/2+B
    & R_p/(M)=C(M)+D
    where A, B, C, and D are constant.
    2) The ratio of the rate constant of the unimolecular cyclization reaction to that of the bimolecular propagation reaction of the uncyclized radical, kckp, was 22.0 mol/l.
    3) The copolymerization of DβMPP proceeded primarily by means of cyclocopolymerization, and the ratio of the cyclization rate to the vinyl propagation also decreased with an increase in the comonomer fraction in the copolymer.
    4) The following reactivity ratios were estimated on the basis of the Smets-Roovers equation: (Remark: Graphics omitted.)
  • Teruaki Mukaiyama, Takanobu Kumamoto, Shinichi Fukuyama, Takeo Taguchi
    1970 Volume 43 Issue 9 Pages 2870-2873
    Published: 1970
    Released: March 27, 2006
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    It was found that vinyl sulfide derivatives were obtained in good yields by the reactions of carbonyl compounds with α-phenylthioalkylidenetriphenylphosphorane. Phosphorane was prepared by the equimolar reaction of alkylidenetriphenylphosphorane and N-phenylthio-N-methylacetamide. It was established that, differing from the case of alkylidenetriphenylphosphorane, di-methyloxosulfonium methylide reacted with N-phenylthiophthalimide and N-phenylthiosuccin-imide to give N-bis(phenylthio)methylphthalimide and N-bis(phenylthio)methylsuccinimide, re-specitively.
  • Mitsuhisa Shimada, K\={o}ji Takeuchi, Yoshiya Asai, Shigeru Kuwata, Hi ...
    1970 Volume 43 Issue 9 Pages 2874-2877
    Published: 1970
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    DL-β-(5-Cytosinyl)-α-alanine and its dipeptides with glycine were synthesized. The benzyloxycarbonylation of this amino acid afforded the α-N-substituted derivative, but all attempts to obtain the diacylated derivative were unsuccessful. The condensation of the benzyloxycarbonyl derivative with glycine ethyl ester by the carbodiimide method afforded the expected dipeptide, though the yield was low (18%); it was accompanied by a large amount of a bicyclic compound, a lactam produced by an intramolecular acylation. The ethyl ester hydrochloride of this amino acid could not be obtained in a pure state, probably because of its ready cyclization to the same lactam structure under weakly acidic conditions. This complication could be avoided by using the tertiary butyl in place of the ethyl ester. Benzyloxycarbonylglycine p-nitrophenyl ester was condensed smoothly with this ester, affording the expected dipeptide in a 53% yield. The carbodiimide method could also be used, but it was less effective.
  • Abdel-Monem El-Refai, Lotfy Sallam, Ismail El-Kady
    1970 Volume 43 Issue 9 Pages 2878-2884
    Published: 1970
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Hydroxylation of progesterone with Rhizopus nigricans REF 129 at C-l1, C-6, C-17, C-21 as well as formation of 11α-hydroxy-5α-pregnane-3,20-dione was investigated when the fermentation medium was modified in a different manner. The various transformation products of progesterone were found to be affected qualitatively and quantitatively by the composition of the medium employed. Mg2+, PO43− proved to be indispensable for the transformation processes. Mn2+ and Fe2+stimulated the reactions. Similarly, acetate, malate and riboflavin enhanced the transformation processes. Formation of the various derivatives of progesterone, except for 11α-hydroxy-5α-pregnane-3,20-dione and 6β, 11α-dihydroxyprogesterone, was also favoured by the addition of adenine, adenosine, uracil and guanine to the fermentation medium.
  • Yoshiyuki Kawase, Tomoko Okada, Toshio Miwa
    1970 Volume 43 Issue 9 Pages 2884-2890
    Published: 1970
    Released: March 27, 2006
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    The acetylation of methyl 2,3-dimethyl-4- and -7-benzofurancarboxylates was carried out by the action of acetyl chloride and aluminum chloride in carbon disulfide at room temperature to afford the 6-acetyl compounds; these compounds were converted to keto-acids by hydrolysis, and then to the known dicarboxylic acid or to the known 6-acetylbenzofuran. The alkylation of acetyl and methoxycarbonyl derivatives of 2,3-dimethylbenzofuran was carried out by the action of n- or iso-propyl bromide and aluminum chloride in carbon disulfide at reflux temperature, both the bromides furnishing the same isopropylated product. The crude products from the 4-acetyl- and 4-methoxycarbonyl-benzofurans could not be purified, but 2,3-dimethyl-6-isopropyl-4-benzofurancarboxylic acid was obtained by the hydrolysis of the product from the latter. In the cases of 5-acetyl- and 5-methoxycarbonyl-benzofurans, the isopropylation occurred at the 7-position and the products were converted to the same carboxylic acids, while the isopropylation occurred at the 4-position in the cases of 6-acetyl- and 6-methoxycarbonylbenzofurans, and diisopropylation occurred in the case of 7-methoxycarbonylbenzofuran.
  • Katsuyuki Ogura, Teruo Matsuura
    1970 Volume 43 Issue 9 Pages 2891-2893
    Published: 1970
    Released: March 27, 2006
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    Mechanism for the photochemical transformation of a 2,5-cyclohexadienone into a bicyclo[3.1.0]hex-3-en-2-one (so-called lumiketone) was discussed. Photolysis of 2,4,6-tri-t-butyl-4-methoxy-2,5-cyclohexadienone (VII) gave only one stereoisomer (VIIIa) of the corresponding lumiketones. This fact and the prediction by the Woodward-Hoffmann rule indicate that a biradical-like excited state XI with 3,5-bonding gives rise to a direct rearrangement to lumiketone Villa as shown in Path B (Scheme II).
  • Tadashi Sasaki, Ken Kanematsu, Akikazu Kakehi
    1970 Volume 43 Issue 9 Pages 2893-2899
    Published: 1970
    Released: March 27, 2006
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    The formation of substituted N-ethoxycarbonyl-1(1H)-azepine derivatives is reinvestigated in the thermal reactions of benzene derivatives with ethyl azidoformate. The rate-determining step in these reactions is determined by kinetic experiments to be the decomposition of the azide. The (4+2) π cycloadducts of these azepine derivatives are obtained by thermal reactions with tetracyanoethylene (TCNE) as a dienophile. The formation of compounds 22, 23, 24, 25, 26, and 27 is confirmed by the spectral evidence.
  • Norio Nishi, Seiichi Tokura, Junzo Noguchi
    1970 Volume 43 Issue 9 Pages 2900-2907
    Published: 1970
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Benzoyl-arginine-p-nitroanilide (BAPA) is a synthetic substrate for trypsin, papain, and other enzymes, but it has not yet been prepared in the active L-form, although the preparations of DL-form and D-form by the trypsin digestion of the DL-form have been reported. The optically active L-BAPA was prepared by the following route; Nα-carbobenzyloxy-Nω-nitro-L-arginine-p-nitroanilide was prepared from Nα-carbobenzyloxy-Nω-nitro-L-arginine and p-nitrophenyl isocyanate, and the subsequent decarbobenzyloxylation and the benzoylation of this compound gave Nα-benzoyl-Nω-nitro-L-arginine-p-nitroanilide. The removal of the nitro group was followed by Sakakibara’s method using hydrogen fluoride. The L-BAPA shows the same melting point and the same reversal optical rotation as those of D-BAPA. When Nα-benzoyl derivatives of L-arginine were used as starting materials in the preparation of BAPA, DL-BAPA was always obtained with complete racemization; when Nα,Nω,Nω′-tricarbobenzyloxy-L-arginme as the starting material reacted on p-nitrophenyl isocyanate, the product had no racemization, but the desired L-BAPA was not obtained because one of the carbobenzyloxy groups on the guanido group was extraordinally stable to reagents and could not be removed completely.
  • Taiiti Okada, Koiti Kamogawa, Mituyosi Kawanisi, Hitosi Nozaki
    1970 Volume 43 Issue 9 Pages 2908-2911
    Published: 1970
    Released: March 27, 2006
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    Irradiation of bicyclo[3.1.0]hexane-2,4-diones affords isomeric enol lactones retaining the cyclopropane ring. In contrast, photoreaction of 6,6-dimethylspiro[2.5]octane-4,8-dione in ethanol results in the formation of an isomeric benzofuran derivative and dimedone-acetaldehyde condensation product. Cleavage of the cyclopropane ring is characteristic of the behavior of the latter β-diketone.
  • Norio Yoshida, Tetsuo Kato, Nobuo Izumiya
    1970 Volume 43 Issue 9 Pages 2912-2919
    Published: 1970
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    An N-terminal nonapeptide fragment of bovine trypsinogen, H-L-Val-L-Asp-L-Asp-L-Asp-L-Asp-L-Lys-L-Ile-L-Val-Gly-OH, was synthesized via two routes and its susceptibility with trypsin was investigated. Protected derivatives, t-butyloxycarbonyl protected nonapeptide t-butyl ester and benzyloxycarbonyl protected nonapeptide benzyl ester, were prepared by stepwise elongation. Removal of the protecting groups was carried out by treatment with trifluoroacetic acid and hydro-genation respectively. The naked peptide was purified with chromatography on ECTEOLA cellulose column using dilute acetic acid as a solvent. Upon lyophilization the desired nonapeptide was obtained as colorless powder, a portion of the product being digested with trypsin. Rate of tryptic hydrolysis of the peptide was found to be unexpectedly low in the absence of calcium ion, while considerable acceleration of the hydrolysis by calcium ion was noted.
  • Otohiko Tsuge, Akiyoshi Torii
    1970 Volume 43 Issue 9 Pages 2920-2924
    Published: 1970
    Released: March 27, 2006
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    The dehydrobromination of 9-(1,2-dibromoethyl)acridine, which had easily been obtained by the bromination of 9-vinylacridine, to 9-ethynylacridine was attempted by several methods, and it has been established that this transformation can be effected in a 55% yield by the use of methanolic potassium hydroxide in dioxane. It has been found that the reaction of 9-ethynylacridine with p-nitrosodialkylaniline under the influence of hydrochloric acid in ethanol leads to the formation of the corresponding 1-(9-acridinyl)-1,2-bis(p-dialkylaminophenylimino)ethane N1,N2-dioxide. In addition, the configuration of the dioxide has also been proposed on the basis of spectroscopic studies and an inspection of the Dreiding models.
  • Akio Sakurai, Hiroshi Midorikawa, Yasuo Hashimoto
    1970 Volume 43 Issue 9 Pages 2925-2933
    Published: 1970
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Various substituted benz[f]isoquinolines were readily prepared by the condensation of ethyl cyanoacetate and salicylaldehyde or 3-methoxysalicylaldehyde with aliphatic ketones (acetone, diethyl ketone, methyl pentyl ketone, methyl isopentyl ketone, etc.) or aromatic ketones (acetophenone, o-hydroxyacetophenone, m-nitroacetophenone, propiophenone, etc.) in the presence of ammonium acetate. On the other hand, condensation with cyclic ketones such as cyclopentanone and cyclohexanone gave benz[f]cyclopent[c]isoquinolines and benzo[k]phenanthridines respectively.
  • Yoshio Kohara, Michio Kobayashi, Hiroshi Minato
    1970 Volume 43 Issue 9 Pages 2933-2937
    Published: 1970
    Released: March 27, 2006
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    N,N′-Diarenesulfonylhydrazine was oxidized with several oxidizing regents, but diarenesulfonyl diimide was not isolated. Diarenesulfonyl diimide produced immediately decomposed with evolution of 1 mol of nitrogen, and afforded the corresponding sulfonyl bromide, α-disulfone and sulfonic acid. Plausible mechanisms of decomposition were discussed.
  • Masataka Yokoyama
    1970 Volume 43 Issue 9 Pages 2938-2941
    Published: 1970
    Released: March 27, 2006
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    1,2-Dithiole-3-thiones and 1,2,4-trithioles were synthesized by the reaction of α-cyanodithiocarboxylate, hydrogen sulfide, and bromine water. The reaction mechanism and the mass spectra of 1,2-dithiole-3-thiones were discussed.
  • Muneji Miyoshi, Terutoshi Kimura, Shumpei Sakakibara
    1970 Volume 43 Issue 9 Pages 2941-2944
    Published: 1970
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    A series of N-protected L-proline oligomers, the di-, tri-, tetra-, penta-, hexa- and octamer, were synthesized by conventional methods. The proline imino-group was protected by the t-amyloxycarbonyl (Aoc) group, and the carboxyl group was protected as the benzyl ester during the synthesis. These Aoc-oligoprolines were valuable in elucidating the relationship between the conformation and the degree of polymerization of the polyprolines. The Aoc-protecting group was useful in purifying the intermediates and in obtaining crystals of the final compounds.
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