Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 44 , Issue 12
Showing 1-50 articles out of 79 articles from the selected issue
  • Katsutaka Sasaki, Kiyoshi Arakawa
    1971 Volume 44 Issue 12 Pages 3223-3226
    Published: 1971
    Released: March 27, 2006
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    Ultrasonic experiments for aqueous solutions of amino acids (glycine, l-alanine, l-valine, and l-leucine) were carried out by means of pulse technique in order to study the nature of solute-solvent interactions. The sound velocity and absorption coefficient were determined for aqueous solutions in the frequency range 15–45 MHz, at temperatures 10–30°C. No relaxation frequency was observed in all the solutions. The absorption coefficient for glycine solutions at low concentrations is nearly equal to that for pure water. The result is consistent with the idea that glycine molecules behave as a structure breaker within water. Concerning the concentration dependency of sound velocity and absorption, no appreciable difference is observed in various solutions of amino acids in spite of difference in the size of hydrocarbon side chains in solute molecules. It is concluded that the behavior of l-alanine and its higher homologues in water dose not differ from that of glycine.
  • Masamoto Iwaizumi, Shozo Kubota, Taro Isobe
    1971 Volume 44 Issue 12 Pages 3227-3229
    Published: 1971
    Released: March 27, 2006
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    NO2 adsorbed on silica-gel surfaces shows temperature-dependent ESR spectra, which can be explained by assuming a restricted rotation of the NO2 molecule, where the preferred axis is the O–O direction. It is concluded from this observation that a hydrogen-bond force between the oxygen of NO2 and OH groups on the silica-gel surfaces plays a part in the NO2-silica-gel interaction. It is also estimated, from the observed hyperfme tensor, that the ONO angle may become slightly smaller when NO2 is adsorbed onto the silica-gel surface from the gas phase.
  • Masao Hashimoto, Michiko Hashimoto, Taro Isobe
    1971 Volume 44 Issue 12 Pages 3230-3232
    Published: 1971
    Released: March 27, 2006
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    The orientation-dependent potential energy of the ethylene crystal was calculated using a somewhat modified expression for the dispersion energy in the case of non-axially symmetric molecules. It was concluded that the main force which determines the angle between the bc plane and the C=C bond axis in the ethylene crystal is the dispersion; on the other hand, it is the quadrupole-quadrupole interaction which determines the angle between the ab plane and the C=C bond axis. The expected molecular arrangement in the crystalline ethylene belongs to the space group P21/n, this is consistent with the conclusion obtained from the spectroscopic data.
  • Yuko Soma
    1971 Volume 44 Issue 12 Pages 3233-3236
    Published: 1971
    Released: March 27, 2006
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    The ultraviolet absorption spectra of olefins adsorbed on the platinum catalyst supported on silica were studied. By comparing the absorption bands of olefins adsorbed on the platinum catalyst with the chrage-transfer bands of platinum-olefin complexes, the observed bands could be interpreted as being due to the electronic transition from filled platinum 5d orbitals to the empty π* orbital of adsorbed olefins.
  • Makoto Misono, Yukio Yoneda
    1971 Volume 44 Issue 12 Pages 3236-3241
    Published: 1971
    Released: March 27, 2006
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    Double-bond isomerization of n-butenes over several supported acidic metal salts such as metal sulfates, perchlorates and phosphates including free acids has been investigated at 60°C with the butene pressure of 14 cmHg. The activity and the selectivity of cis-trans isomerization over double-bond migration increased monotonously, as the acid strength of catalysts increased. Acid strength, activity and selectivity of metal salt catalysts increased with the electronegativity of metal ion where free acids were the most strongly acidic and active catalysts (H+>Al3+>Ni2+>Mg2+>Na+), and for a given metal ion they increased with the acid strength of the conjugated acid (ClO4>SO42−PO43−CH3COO). The activity and selectivity were explained on the basis of a sec-hutyl carbonium ion mechanism which appears more concerted over weak acids. The active sites for the reaction were suggested to be protonic acid sites closely connected to acid radical.
  • Ayao Kitahara, Tadashi Fujii, Seiji Katano
    1971 Volume 44 Issue 12 Pages 3242-3245
    Published: 1971
    Released: March 27, 2006
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    The effect of particle size and capillary radius on electrokinetic potential (ζ-potential) was studied in order to check the influence of overlapping of the electrical double layer and radius effect on the measured ζ-potential by the streaming potential method. The streaming potential was measured with varying particle size and capillary radius of glass in the benzene solution of (C4H9)4NI. The measurement was carried out over the range where the laminar flow and the Quincke’s law hold. The surface conductance was corrected experimentally. ζ-Potential increased with increase of the particle size in the glass column. It was unsuccessful to obtain the ζ-potential independent of the reduced radius of the capillary pore with the Oldham’s treatment. ζ-Potential increased with increase of the capillary radius. The increase was elucidated by the Wood’s method using the appropriate constants, and the constant ζ-potential which was not affected by the capillary radius was obtained. The value was still different from that obtained by the electrophoretic method, but the difference was considerably small as compared with the previous data.
  • Kinzo Tsutsumi, Kazuko Aoki, Haruo Shizuka, Toshifumi Morita
    1971 Volume 44 Issue 12 Pages 3245-3250
    Published: 1971
    Released: March 27, 2006
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    Measurements of the acidity constants in the ground (pKa(S0)), the lowest excited singlet (pKa(S1)), and triplet states (pKa(T1)) for 2-, 3-, 4-, and 9-phenanthrylamines have been carried out by spectrophotometry. The pKa values obtained were in the order of pKa(S0)>pKa(T1)>pKa(S1). The absorption and emission spectra of the phenanthrylamines were compared with the results of the calculations by means of the semi-empirical SCF-MO-CI method. A linear relationship between the pKa values and the net charge (or charge densities) in the ground and excited states was obtained both experimentally and theoretically.
  • Kazuo Tajima, Makio Iwahashi, Tsunetaka Sasaki
    1971 Volume 44 Issue 12 Pages 3251-3254
    Published: 1971
    Released: March 27, 2006
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    The radio- and surface-chemically pure nonionic surfactant, C10H21(CHT)2O(C2H4O)6H, was synthesized, and surface tension and adsorbed amount of its aqueous solution were measured directly at the air-solution interface at 30°C. Surface tension was measured by the drop-volume and Wilhelmy plate methods, while adsorbed amount was measured by the radiotracer method. The adsorption isotherm showed saturation values of 2.73×10−10 mol/cm2 above the concentration of about 1/5 of the critical micelle concentration. The observed amount of adsorption was in good agreement with the values calculated from surface tension data measured by the Wilhelmy plate method by applying the Gibbs adsorption isotherm for a single solute system. The time dependence of surface tension of surfactant solution was further discussed, and the inherent time dependence was shown for pure surfactant solution.
  • Shunsuke Meshitsuka, Hiroaki Takahashi, Keniti Higasi
    1971 Volume 44 Issue 12 Pages 3255-3259
    Published: 1971
    Released: March 27, 2006
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    Infrared spectra of Li2SO4·H2O and Li2SO4·D2O have been measured from 4000 to 30 cm−1 at room temperature and liquid-nitrogen temperature. Librational bands of the water of crystallization have been observed and the modes of libration are discussed. The normal coordinate analysis of the crystal as a whole has been performed and the observed bands are interpreted. Translational bands of H2O and librational bands of SO4 are also discussed.
  • Yutaka Kubokawa, Hisashi Miyata, Yoshihiko Uegaki
    1971 Volume 44 Issue 12 Pages 3259-3264
    Published: 1971
    Released: March 27, 2006
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    Infrared spectra of various pyrolyzed polyacrylonitrile and of deuterated formic acids (HCOOD, DCOOH, and DCOOD) adsorbed on it were investigated. The effect of pyrolysis temperature upon the decomposition products of formic acid adsorbed on the polymer was studied. It was found that parallelism exists between the concentration of the conjugated nitrile group and the percentage of the decomposition of formic acid adsorbed, leading to the conclusion that the active sites for the decomposition reaction are associated with the conjugated nitrile group in the case of polyacrylonitrile pyrolyzed below 300°C. On the other hand, there was a close correlation between the activity for decomposition and the number of free spins in the polymer pyrolyzed above 350°C.
  • Shin-ichi Ohno, Akihisa Sakumoto, Teikichi Sasaki, Kiyoshi Kawatsura, ...
    1971 Volume 44 Issue 12 Pages 3265-3268
    Published: 1971
    Released: March 27, 2006
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    Aerated aqueous solutions of methylene blue (MB+; 3×10−7 M) were subjected to 60Co-γ rays in the presence of added methanol, ethanol, or D-glucose at dose rates up to 4×1015 eV g−1s−1, and the change in the optical absorption spectrum in the 300–700 nm region was studied using a rapid-scan spectrophotometer (scanning speed: 30 ms/100 nm). In the presence of high concentrations (>10−2 M) of organic substances, it was found that radiation caused a decrease in the absorption due to MB+ at 650 nm (the magnitude of the decrease was proportional to the radiation intensity), and that, on the removal of the radiation source, the original absorption spectrum was restored. This was interpreted as meaning that the radiation-produced leuco-form of methylene blue (MBH) was rapidly oxidized by oxygen. The rate constant, k(MBH+O2), was estimated to be (0.6±0.2)×104 M−1S−1 at neutral pH. In the absence of added organic substances, the permanent decoloration of MB+ took place; this was interpreted as being due to the reaction of MB+with OH-radicals. From the competition kinetic study using 10−4 M methanol, the rate constant, k(OH+MB+), was estimated to be 1.1×10−10 M−1S−1.
  • Mizuka Sano, Koichi Ohno, Hideo Akamatu
    1971 Volume 44 Issue 12 Pages 3269-3271
    Published: 1971
    Released: March 27, 2006
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    The thermoelectric power of N,N′-diphenyl-p-phenylenediamine·I2, N,N′-di-β-naphthyl-p-phenylenedia-mine·I3.5, phenothiazine·I3, and N-methylphenothiazine·I3 was measured in the temperature range from −35 to 140°C. The observed power for each complex was explained by means of the mechanism of mixed conduction of electrons with holes, and the ratio of electron-conduction to hole-conduction was estimated as a function of temperature. In the iodine complexes of the substituted p-phenylenediamines the conductivity due to electrons is found to be larger than that due to holes, while in phenothiazine·I3 holes contribute more to the conductivity. In N-methylphenothiazine·I3, the hole-conduction is predominant in the higher temperature region and the electron-conduction in the lower temperature region.
  • Akira Nakajima
    1971 Volume 44 Issue 12 Pages 3272-3277
    Published: 1971
    Released: March 27, 2006
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    The anomalously large Ham effect observed in pyrene has been studied in various solvents at room temperature by measuring the fluorescence and absorption spectra. As in the case of benzene, the Ham bands of pyrene were assigned to the 0–0 and ag-vibration bands. This was confirmed by fluorescence polarization measurement. The correlation of the intensities of the fluorescence and absorption bands to solvent polarities is discussed.
  • Isao Suzuki
    1971 Volume 44 Issue 12 Pages 3277-3287
    Published: 1971
    Released: March 27, 2006
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    The vibrational energy levels of diatomic molecules are related with the harmonic and anharmonic force constants by solving the vibrational Hamiltonian matrix numerically. The associated rotational levels are computed by two different methods; (1) perturbation treatment which utilizes the wave functions obtained, and (2) direct numerical diagonalization of the vibration-rotation submatrices. This approach, combined with the least-squares procedure, is applied to the determination of anharmonic force constants for CO and HCl molecules. Special attention is paid to the truncation effect of potential functions upon the calculated energy levels. Limitations in the usual perturbation method as well as the applicability of the present method to triatomic molecules are discussed.
  • Keiichi Egawa, Nobuaki Nakashima, Noboru Mataga, Chiyoe Yamanaka
    1971 Volume 44 Issue 12 Pages 3287-3292
    Published: 1971
    Released: March 27, 2006
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    Time-resolved CT (charge transfer) fluorescence spectra and the fluorescence rise and decay curves at various wavelengths of the CT fluorescence band have been measured for the 1,2,4,5-tetracyanobenzene (TCNB)–toluene system at various temperatures. The results and detailed studies of the effect of solvent polarity on the fluorescene wavenumbers have demonstrated that the relaxation process is due to the change of structure including the surrounding solvent molecules from the Franck–Condon (F.C.) state to the equilibrium (e.q.) state of the excited complex. This relaxation process causes a large Stokes shift of the CT fluorescence.
  • Masatoki Yokoi, Kashiro Kuroda
    1971 Volume 44 Issue 12 Pages 3293-3295
    Published: 1971
    Released: March 27, 2006
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    The electrolytic conductances of bis(halogenoacetato)bis(ethylenediamine)cobalt(III) perchlorate, [Co(halac)2(en)2]ClO4 where Hhalac=CH3CO2H, CH2ClCO2H, CHCl2CO2H, CCl3CO2H, and CF3CO2H were measured in water at 25°C. The equivalent conductances of the solutions (c=10−3–10−4 mol/l) were obtained from the conductance kinetic runs by extrapolating conductances to time zero. The ionic equivalent conductances of the complex ions were 21.5–17.2 ohm−1cm2eq.-−1. and decreased with the increase of the chlorine content in the chloroacetato ligands. Little differences in the ionic equivalent conductances were observed between a pair of cis and trans isomers. The rate constants of the first order aquation of the complexes were estimated.
  • Masatake Ohmasa, Minoru Kinoshita, Hideo Akamatu
    1971 Volume 44 Issue 12 Pages 3296-3298
    Published: 1971
    Released: March 27, 2006
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    o-Phenylenediamine and tetracyano-p-quinodimethane (TCNQ) were shown to form two types of solid complexes with compositions of 1 : 1 and 2 : 1. The 2 : 1 complex is essentially of ionic type, while the 1 : 1 complex is characterized as of non-bonding type from the analysis of its infrared absorption spectrum. It was shown that the difference in type is reflected on the magnetic and electrical properties of these complexes. The ESR absorption or the spin concentration of the 1 : 1 complex changed irreversibly with grinding or heat-treatment (70°C), while no appreciable change was observed in the 2 : 1 complex with these treatments. The electrical resistivity is lower for the 1 : 1 complex than the 2 : 1 complex by a factor of 102. From these observations, it is considered that the ground state electronic structure of the 1 : 1 complex is in a similar situation to those of diaminopyrene-chloranil and benzidine-TCNQ complexes.
  • Shuji Emori, Motomichi Inoue, Masaji Kubo
    1971 Volume 44 Issue 12 Pages 3299-3304
    Published: 1971
    Released: March 27, 2006
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    The magnetic susceptibilities of diisothiocyanatobis(thiourea)nickel(II), diisothiocyanatobis(N,N′-dimethyl-thiourea) nickel(II), diisothiocy anatobis(2-thioimidazolidinone)nickel(II), diisothiocyanatobis(2-thiopyrrolidone)nickel(II), and diisothiocy anatobis(thioacetamide)nickel(II) were observed between the liquid-helium temperature and room temperature. Except for the second complex, antiferromagnetic interaction operates between one-dimensional nickel chains, within each of which ferromagnetic spin coupling exists. The exchange integrals, J within a chain and J′ between chains, were evaluated on the basis of the coupled-double-chain model and the molecular-field model. The absence of interaction between chains in the crystals of the second complex can be accounted for by the presence of bulky N,N′-dimethylthiourea molecules between chains. The antiferromagnetic interactions between chains in the crystals of other complexes are attributable to the presence of bridging arrangements between chains, as is indicated by X-ray analysis.
  • Isao Mochida, Yasuhide Anju, Hiroko Yamamoto, Akio Kato, Tetsuro Seiya ...
    1971 Volume 44 Issue 12 Pages 3305-3310
    Published: 1971
    Released: March 27, 2006
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    The elimination reactions of haloethanes and halopropanes on solid acids and bases, including a series of metal sulfates supported by silica gel, were studied at 300°C by means of the pulse technique in order to clarify the mechanism of the catalytic dehydrohalogenation. The trans-1,2-dichloroethylene/cis-1,2-dichloroethylene (trans-1,2/cis-1,2) selectivities from 1,1,2-trichloroethanes as well as the activities of the metal sulfates supported by silica gel were well correlated with the electronegativities of the metal ions. Generally speaking, the rates of the dehydrochlorination from chloroalkanes were nearly equal to those of the dehydrobromination from bromoalkanes on the solid acids, but the latter were larger than the former on solid bases. The reactivities of the alkylhalides on solid acids and bases were examined from the electronic view-point, and we tried to correlate them with some reactivity indexes. A kinetic isotope effect with regard to hydrogen was observed on solid bases, but not on solid acids, in the dehydrobromination of 1,2-dibromoethane. From these facts, it was concluded that the dehydrohalogenation proceeds through a carbonium-ion mechanism on solid acids and via an E2 step-by-step mechanism on solid bases.
  • Hiroshi Masuhara, Motoo Shimada, Nobuyuki Tsujino, Noboru Mataga
    1971 Volume 44 Issue 12 Pages 3310-3316
    Published: 1971
    Released: March 27, 2006
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    Dynamic behaviors of the weak electron donor-acceptor (EDA) complex in its lowest excited singlet state have been investigated by the nsec flash photolysis method and measurements of fluorescence and transient photocurrent. In polar solvents the weak EDA complex in its lowest excited singlet state dissociates spontaneously into ions. The dynamic behaviors of s-tetracyanobenzene(TCNB)-benzene and TCNB-toluene complexes were studied in some solvents and the existence of the direct radiationless process at the excited Franck-Condon (FC) state as well as in the course of relaxation process from the excited FC state to the fluorescent state has been confirmed in the case of 1,2-dichloroethane solution. The nature of the intra-complex radiationless processes was discussed on the basis of this result. It has been pointed out that the lifetime of excited states is of crucial importance for understanding the dynamic behaviors of excited weak EDA complexes.
  • Tsunetake Fujiyama
    1971 Volume 44 Issue 12 Pages 3317-3323
    Published: 1971
    Released: March 27, 2006
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    Infrared and Raman spectra of XCH2CH2CN-type molecules (X=CH3, Cl, and Br) are studied. From the spectral analysis, it is concluded that trans and gauche isomers coexist in the liquid phase, the gauche being more stable. It is also shown that these molecule take gauche configurations in the crystalline phase.
  • Kozo Inuzuka, Ralph S. Becker
    1971 Volume 44 Issue 12 Pages 3323-3328
    Published: 1971
    Released: March 27, 2006
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    Potential energy curves as a function of the angle of twist around single and double bonds have been calculated for piperylene (1,3-pentadiene). Also, direct-excitation cistrans photoisomerization and trans→methycyclobutene photochemistry have been investigated as a function of the temperature. The theoretical analysis strongly indicates that the cyclobutene is formed photochemically from the trans-s-cis isomer which is created thermally from the trans-homer in the ground state (not by photoisomerization). The temperature-dependency data support this conclusion. The theoretical data also indicate that there is a small barrier to photoisomerization around the double bond in the first excited singlet (and triplet) state. The temperature-dependency data also support this conclusion. The potential energy curves are in harmony with the known emission (none exists), photoisomerization, and internal-conversion data for the cis- and trans-piperylenes. The emission properties of model cyclic diene steroids are compared with those expected from linear dienes, and the emission results of the former are interpreted within the theoretical framework developed.
  • Gunzi Saito, Yoshio Matsunaga
    1971 Volume 44 Issue 12 Pages 3328-3335
    Published: 1971
    Released: March 27, 2006
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    o-Chloroaniline, m-nitroaniline, 3-nitro-4-methylanilme, and N,N-dimethylamino-p-benzaldehyde form true phenolates with picric acid. However, their electronic and vibrational spectra were found to be drastically modified by melting. The appearance of a new electronic absorption located near the place where the corresponding s-trinitrobenzene complex exhibits the charge-transfer band is noted above the melting point. At the same time, the vibrational bands due to the anilinium ion observed at room temperature are replaced by those due to the aniline. On the basis of these observations, it was concluded that complex isomerization from a true phenolate to a charge-transfer complex takes place by melting in these cases. On the other hand, the spectra of N,N-diethylanilinium and m-chloroanilinium picrates were shown to remain the same below and above the melting points.
  • Akinori Hasegawa, Yoshio Yamada, Masaji Miura
    1971 Volume 44 Issue 12 Pages 3335-3340
    Published: 1971
    Released: March 27, 2006
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    The ESR spectra of aqueous solutions of binuclear vanadyl tartrates remarkably varied with their pH values. This variation was found to be directly correlated with the change in the form of the carboxyl group, i.e. whether it was dissociated or acidic. Thus, the frozen solution spectra were observed in water-ethylene glycol at 77°K and analyzed in terms of several magnetic parameters containing the parameter of magnetic dipolar interaction, D. From these D values, the intramolecular V···V distances were estimated to be ca. 4.2, 5.2, and 6.5Å in the solutions at pH 9, 4.8, and 2.8 respectively. Such a remarkable change in the V···V distances as interpreted to be caused by the dissociation of the coordinate bonds between the vanadium atom and the carboxyl oxygen atom and the change in the molecular structure of the tartrates, brought about the change in the form of the carboxyl groups.
  • Yoshio Ito, Shunsuke Shishido
    1971 Volume 44 Issue 12 Pages 3341-3344
    Published: 1971
    Released: March 27, 2006
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    This paper has aimed at the revelation of the thickening mechanism of a latex on the addition of alkali. Experiments have been made on two kinds of latexes dialyzed thoroughly, i.e., the butadiene–methyl methacrylate copolymer latex and the butadiene-methyl methacrylate–methacrylic acid copolymer latex. The degree of the swelling of the latex particles on the addition of alkali has been correctly obtained and has been connected with the thickenability of the latex. The results provide a more rigorous description than Wesslau’s suggestion that the thickening of a latex on the addition of alkali is ascribed to the swelling of the latex particles alone. The reason why NH4OH is a proper thickener is presented, and the most suitable amount of alkali for the thickening of a latex is discussed.
  • Yôichi Iida
    1971 Volume 44 Issue 12 Pages 3344-3347
    Published: 1971
    Released: March 27, 2006
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    The semiconductive organic crystal of [(C6H5)3PCH3]+(TCNQ)2 is known to undergo a first-order phase transition at 315.7°K. The discontinuity in the temperature dependence of the electrical conductivity takes place at the transition temperature, above which the populations of the electrons and the holes in the electrical conductivity increase abruptly. A theoretical consideration of the system of conduction carriers in an intrinsic semiconductor was developed in order to evaluate the entropy change of the electrons and holes at the phase transition. For [(C6H5)3PCH3]+ (TCNQ)2, this kind of entropy change was found to be much less than the total entropy change determined from the heat-capacity measurements by Kosaki et al. In view of these results, it was concluded that the anomaly in the electrical conductivity was induced by the change in the crystal structure.
  • Hiromitsu Moriya, Tatsuya Sekine
    1971 Volume 44 Issue 12 Pages 3347-3352
    Published: 1971
    Released: March 27, 2006
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    The formation and extraction equilibria of zinc(II) complexes with thiocyanate ions have been determined at 25°C. Zinc(II) ions in 1 m sodium perchlorate constant ionic media containing thiocyanate ions at various concentrations have been extracted into chloroform containing β-isopropyltropolone (IPT), into hexane containing trioctylphosphine oxide (TOPO), or into methyl isobutyl ketone (MIBK). The stability constants of the zinc(II) thiocyanate complexes in the aqueous phase were first determined from the decrease in the IPT chelate extraction, and then the distribution constants for the zinc(II) thiocyanate complexes into the latter two solvents were determined. The results were explained by saying that (i) zinc(II) forms the first (logβ1=0.56), second (logβ2=1.32), and the third (logβ3=1.18) complexes in the above aqueous phase, (ii) TOPO in hexane extracts the second complex as an adduct in the Zn(SCN)2(TOPO)2 form, (iii) MIBK extracts both the second and the third complexes, and (iv) the addition of sodium perchlorate causes a salting-in effect in the lower-ligand-concentration region. Some discussion was made of the dissociation of ion-pairs in the organic phase.
  • Takashi Komorita, Jinsai Hidaka, Yoichi Shimura
    1971 Volume 44 Issue 12 Pages 3353-3363
    Published: 1971
    Released: March 27, 2006
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    Square planar complexes of [ML2] type were synthesized, where M=Pd2+ and Ni2+ for L=L-valine-, L-phenylalanine- and L-proline-amidate anions, and M=Pd2+, Ni2+ and Cu2+ for L=L-leucinemethylamidate anion and for L2=trimethylenediamine-N,N′-diisobutyric acid amidate dianion; the last ligand is a tetradentate one and gives exclusively cis type complexes. Cis and trans isomers were isolated and identified for each of the L-valinamidato and the L-prolinamidato palladium complexes. All the other complexes were inferred to be trans isomers from examination of the electronic absorption and circular dichroism spectra. Common solvent effects of the ligand field bands were clearly observed between the trans palladium and trans nickel complexes. A similar empirical relationship was also found between the ligand field bands of the trans palladium complexes and those of the corresponding cis isomers. The spectral behavior of the bis(L-amino-acid-amidato)-copper(II) complexes was not so easily related to that of the corresponding nickel or palladium complexes. The ligand field bands of the palladium, nickel, and copper complexes were tentatively assigned.
  • Kousaburo Ohashi, Katsumi Yamamoto, Toshio Suzuki, Yoshimi Kurimura
    1971 Volume 44 Issue 12 Pages 3363-3366
    Published: 1971
    Released: March 27, 2006
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    The solvent effect on the reduction of the textitcis-chloro-2-aminoethanolbis(ethylenediamine)cobalt(III) ion by iron(II) was investigated in aqueous solutions of dimethylsulfoxide (DMSO), dimethylformamide (DMF), ethanol, and acetone. The second-order rate constants for the reduction are 4.4×10−5 M−1sec−1 in the absence of an organic solvent, 1.4×10−3 M−1sec−1 in 0.20 Mf DMSO, 7.3×10−4 M−1sec−1 in 0.20 Mf DMF, 1.1×10−4 M−1sec−1 in 0.20 Mf ethanol, and 1.0×10−4 M−1sec−1 in 0.20 Mf acetone, at 25°C and at 0.16 M HClO4 and Σ[ClO4]=0.60 M (Mf= mol fraction of organic solvent). From the kinetic and spectral data, it is suggested that the increase in the rate upon the addition of an organic solvent may be mainly due to a change in the solvation sphere of the reductant by replacing the water molecules by the organic molecules.
  • Yoshimi Kurimura, Ikuko Meguro, Kousaburo Ohashi
    1971 Volume 44 Issue 12 Pages 3367-3369
    Published: 1971
    Released: March 27, 2006
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    The reductions of chloro- and bromo(ethylenediaminetriacetatoacetic acid)cobaltate(III), chloro- and bromo (N-hydroxy ethy lethy lenediamine-N,N′, N′-triacetato)cobaltate (III), and dichloro(ethylenediaminediacetato) cobaltate(III) ions by iron(II) in perchloric acid solutions obey the second-order rate expression: –d-[Co(III)]/dt=kc[Co(III)][Fe2+]. The second-order rate constants, kc, and activation parameters for these reactions were determined spectrophotometrically. For the cases of all the Co(III) complexes investigated, an increase in the rate constant with the hydrogen-ion concentration at a constant ionic strength is expressed by: logkc=logk0+A[H+], where k0 and A are constants for the given complex at a constant ionic strength and temperature. The hydrogen-ion dependence can be explained by the difference in the degree of stabilization of the Co(III) anion between that by hydrogen ions and that by sodium ions.
  • Yasuaki Shimoishi
    1971 Volume 44 Issue 12 Pages 3370-3372
    Published: 1971
    Released: March 27, 2006
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    Selenium (IV) reacts with 4-nitro-o-phenylenediamine to form 5-nitropiaselenol, which is detected by means of a gas chromatograph equipped with an electron-capture detector. By this highly sensitive method, the selenium in pure tellurium metal (99.9–99.999%) can easily be determined. Aqua regia oxidizes both selenium and tellurium to the quadrivalent state, and no loss of selenium is found upon this treatment. This method requires only 10–30 mg of a tellurium sample, and the presence of foreign ions does not interfere. It was found that pure tellurium, commercially available, always contains 10−3–10−4% selenium.
  • Yoichi Sasaki, Junnosuke Fujita, Kazuo Saito
    1971 Volume 44 Issue 12 Pages 3373-3378
    Published: 1971
    Released: March 27, 2006
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    The spectroscopic and chemical properties of various μ-peroxo and μ-superoxo cobalt(III) complexes containing several kinds of polyamine including optically active l-propylenediamine (l-pn) have been studied. The single bridged μ-peroxo complexes have strong absorption peaks at ca. 300 nm, whereas the double-bridged μ-peroxo-μ-amido and μ-peroxo-μ-hydroxo complexes have peaks at ca. 350 nm. The μ-superoxo complexes have two absorption peaks in the visible region at ca. 700 and 480 nm. The former is remarkably stronger for singlebridged species, but both are of almost equal strength for double bridged species. The complexes [LNH3Co(μ-O2(2−))CoNH3L]4+ (L; 2en (ethylenediamine), 2l-pn, and trien(triethylenetetramine)) are spontaneously converted into [LCo(μ-O2(2−), OH)CoL]3+ in water at room temperature. The en ligands in [(dien)(en)Co(μO2(2−))Co(en)(dien)]4+ (dien; diethylenetriamine) are replaced by l-pn in a few days in aqueous solutions containing an excess of l-pn. The absolute configuration of [(l-pn)2Co(μ-O2(2−), OH) Co(l-pn)2]3+ is assigned to be ΔΔ on the basis of circular dichroism spectrum.
  • Takashi Matsumoto, Isao Tanaka, Kenji Fukui
    1971 Volume 44 Issue 12 Pages 3378-3382
    Published: 1971
    Released: March 27, 2006
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    The Reformatsky reaction of methyl (+)-α-bromopropionate with benzaldehyde was carried out in order to study the reaction mechanism, and two epimeric methyl 3-hydroxy-2-methyl-3-phenylpropionates (IIa and IIb) were obtained in a 59 : 41 ratio. From a comparison of the optical activity of IIb with that of pure (−)-IIb, it was estimated that lib consists only seven percent of an optically-active compound; this results supports the hypothesis of the enolate anion mechanism. Subsequently, the stereochemistry of this reaction with 2-phenyl-propanal (IV) and 3-phenyl-2-butanone (VIII) was studied. The condensation of IV with methyl bromo-acetate gave a mixture of the epimeric methyl 3-hydroxy-4-phenylvalerates (Va and Vb), which were separated in a 26 : 74 ratio by means of column chromatography on silica gel. Similarly, VIII was also condensed with methyl bromoacetate to give the epimeric methyl 3-hydroxy-3-methyl-4-phenylvalerates (IXa and IXb) in a 31 : 69 ratio. The configurations of these esters were assigned by correlation with the products of the Grignard reaction, the stereochemistry of which is well known. From the present study, it is clear that the Reformatsky and the Grignard reactions of the carbonyl compound having an asymmetric α-carbon atom proceed in a similar fashion; that is, the entering group predominantly approaches the carbonyl group from the least-hindered side. Therefore, Gram’s rule of asymmetric induction can be applied in the stereochemistry of the Reformatsky reaction.
  • Kaichiro Sugita, Shuzi Tamura
    1971 Volume 44 Issue 12 Pages 3383-3387
    Published: 1971
    Released: March 27, 2006
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    The aluminum chloride-catalyzed reactions of cis-Δ4-tetrariydrophthalic acid (1A) and its dimethyl ester (3A) with benzene gave, stereoselectively, t-4-phenyl-cis-bexahydrophthalic acid (2A) and its dimethyl ester (12) respectively. Similarly, the reactions of trans-Δ4-tetrahydrophthalic acid (1B) and its dimethyl ester (3B) with benzene gave, stereoselectively, c-4-phenyWrtrans-hexahydrophthalic acid (2B) and its dimethyl ester respectively, accompanied by a small amount of the c-4,t-2,r-1-isomer. The mechanism can be explained by presuming the interaction of the lone-pair electrons of carbonyl oxygen in the axial carboxyl group with a vacant p-orbital of the carbonium ion, which is produced by protonation to the double bond of the cyclohexenes (1A, 1B, 3A, 3B).
  • Kaichiro Sugita, Shuzi Tamura
    1971 Volume 44 Issue 12 Pages 3388-3391
    Published: 1971
    Released: March 27, 2006
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    The addition reactions of benzene to the double bonds of 4-substituted cyclohexenes, such as 4-benzoyl-cyclohexene (5), 4-acetylcyclohexene (6), methyl 4-cyclohexenecarboxylate (7), and 4-cyclohexenecarboxylic acid (8) have been studied in the presence of aluminum chloride. In all cases, the reactions gave mainly 1,4-disubstituted cyclohexane with the trans configuration stereoselectively. A possible mechanism for this reaction is suggested.
  • Nobuo Izumiya, Masako Muraoka, Haruhiko Aoyagi
    1971 Volume 44 Issue 12 Pages 3391-3395
    Published: 1971
    Released: March 27, 2006
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    Several tripeptides, H-Gly-DL-Ala-B-OH, in which B residues are DL-alanine, L-valine, L-leucine, L-phenyl-alanine, L-proline, and L-serine have been synthesized and the separation of each glycyltripeptide diastereomers by an amino acid analyzer have been studied. Among six peptides studied, diastereomeric mixtures of H-Gly-DL-Ala-L-Val-OH and H-Gly-DL-Ala-L-Leu-OH were separated completely. A procedure to determine the amounts of LL and DL diastereomer of H-Gly-Ala-Leu-OH by the use of the analyzer was developed, and this procedure was applied to examine the influence of coupling reagents for racemization during coupling of benzyl-oxycarbonyl-glycyl-L-alanine and L-leucine benzyl ester by several reagents.
  • Mitsuhiro Kinoshita, Keitaro Ishii, Sumio Umezawa
    1971 Volume 44 Issue 12 Pages 3395-3399
    Published: 1971
    Released: March 27, 2006
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    A new type of antimycin analogs, (3S, 4R, 15S)-4,15-dimethyl-l,5-dioxa-3-(3′-formamidosalicylamido)-cyclopentadecane-2,6-dione (10a) and its (15R)-epimer (10b) have been synthesized. The epimeric fifteenmembered amino-dilactone moieties in 10a and 10b were synthesized from a masked L-threonine and t-butyl DL-10-hydroxyundecanoate. Each of the separated epimeric amino-dilactones was N-acylated with O-benzyl-3-nitrosalicylic acid N-hydroxysuccinimide ester. Hydrogenation followed by N-formylation afforded the anti-fungal substances,10a and 10b. The 10-C-configurations of 10a and 10b were determined as “S” and “R”, respectively. The (15S)-epimer (10a) showed apparently stronger antifungal activity against Piricularia oryzae than that of the (15R)-epimer (10b).
  • Hiroaki Yanagisawa, Mitsuhiro Kinoshita, Sumio Umezawa
    1971 Volume 44 Issue 12 Pages 3399-3405
    Published: 1971
    Released: March 27, 2006
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    Reduction of 3-acetamido-3-C-carboxy-3-deoxy-1,2-O-isopropylidene-α-D-ribofuranose-y-lactone (1) with lithium aluminum hydride or sodium borohydride followed by acetylation gave 3-acetamido-3-C-acetoxymethyl-5-O-acetyl-3-deoxy-1,2-O-isopropylidene-α-D-ribofuranose (2). Hyrdolysis of 2 followed by N-phthaloylation and O-acetylation gave 3-C-acetoxymethyl-5-O-acetyl-3-deoxy-1,2-O-isopropylidene-3-phthalimido-α-D-ribo-furanose (7), which was acetolyzed and chlorinated to give acylglycosyl chloride (9). Condensation of 9 with 6-benzamidopurine followed by aminolysis afforded 9-(3′-amino-3′-deoxy-3′-C-hydroxymethyl-β-D-ribofuranosyl) adenine (11). 6-dimethylaminopurine, guanine, cytosine and uracil derivatives were similarly synthesized.
  • Sango Kunichika, Yasumasa Sakakibara, Tadashi Okamoto, Kentaro Takagi
    1971 Volume 44 Issue 12 Pages 3405-3409
    Published: 1971
    Released: March 27, 2006
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    The carboxylation reaction of propene catalyzed by nickel carbonyl was studied undeer various conditions. Iso- and n-butyric acids were obtained in good yields under mild conditions in the presence of a large amount of an organic acid. The catalytic carboxylation area was examined in detail. The carboxylation reaction proceeded smoothly in tetrahydrofuran, acetic acid, and dioxane. The proportion of isobutyric acid was largest in acetic acid (72.5–77.5%). Triphenylphosphine (TPP) had a great effect on the reaction rate, the catalytic reaction area, and the product distribution. On the reaction mechanism, an active species (HNi(CO)(TPP)X) was taken to account for the experimental results.
  • Tadashi Sasaki, Shoji Egughi, Tsutomu Kiriyama
    1971 Volume 44 Issue 12 Pages 3410-3412
    Published: 1971
    Released: March 27, 2006
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    The pKa values of pseudopelletierine (1), 10-methyl-3,10-diazabicyclo[4.3.1]decan-4-one (2), 10-methyl-3, 10-diazabicyclo[4.3.1]decane (3), 6,8-exo-ethanopseudopelloetierine (4), 7,9-exo-ethano derivatives 5 and 6 of 2 and 3 were measured potentiometrically in water-methyl cellosolve (20 : 80 v/v) at 20°C. The conformational problems in the 3,10-diazabicyclo[4.3.1]decane system were discussed based on the observed pKa′ (pKmcs) values. The characteristic conformational behavior of the monocation (7) of 3 was suggested by the higher value of its pKmcs than of 6.
  • Masahiro Kurabayashi, Koshin Yanagiya, Masahiko Yasumoto
    1971 Volume 44 Issue 12 Pages 3413-3418
    Published: 1971
    Released: March 27, 2006
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    Benziminoethers were formed from benzonitrile and alcohols to the equilibrium extent, and then 3 mol of benziminoethers were reacted with each other to afford triphenyl-1,3,5-triazine at 2–10kbar and 100–120°C. The equilibrium shifted toward benziminoether with an increase in the pressure. The equilibrium constant decreased progressively in the order of methanol>ethanol≈n-propanol≈n-butanol>isopropanol≈sec-butanol, which accords with the increasing number of substituents on the α-position of the alcohols. The formation of triphenyl-1,3,5-triazine obeyed the second-order reaction mechanism and was also retarded in the same order. The reaction was found to proceed in the following manner: Benziminoethers produced by the addition of alcohols to benzonitrile dimerize through a rate-determining step and then trimerized into triphenyl-1,3,5-triazine. The apparent activation volume of the formation of triphenyl-1,3,5-triazine amounted to −31 cm3 mol−1 at 110°C when methanol was used as the alcohol. The accelerating effect of the pressure on the formation of triphenyl-1,3,5-triazine is concluded to be mainly caused by the shift of equilibrium toward benziminoether. Three isomers of cyanopyridine were converted in good yields into the corresponding triazines under high pressure.
  • Michinori Oki, Hiroshi Nakanishi
    1971 Volume 44 Issue 12 Pages 3419-3423
    Published: 1971
    Released: March 27, 2006
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    In alkyl or aryl carbonates, the presence of conformational isomers (s-cis and s-trans) has been confirmed by infrared and nuclear magnetic resonance spectroscopic techniques. The dipole-moment measurements also support the conclusions obtained from the spectroscopic data.
  • Tadashi Endo, Shigeru Noguchi, Teruaki Mukaiyama
    1971 Volume 44 Issue 12 Pages 3424-3426
    Published: 1971
    Released: March 27, 2006
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    Some types of acylurea derivatives were prepared as model compounds for a highly specific organic reaction by molecular association. When ethyl chloroacetate was treated successively with o-aminobenzenethiol (4) and chloroacetyl isocyanate (1) under mild conditions, triacylurea derivative (9) was obtained in total 84% yield. It was found that the use of “amino acid amide and oxalyl chloride” method led to the formation of diacylurea derivative (11) in high yield.
  • Oyo Mitsunobu, Masahiko Eguchi
    1971 Volume 44 Issue 12 Pages 3427-3430
    Published: 1971
    Released: March 27, 2006
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    The reaction of dibenzyl hydrogen phosphate with alcohols in the presence of diethyl azodicarboxylate and triphenylphosphine, followed by catalytic hydrogenation, resulted in the formation of the corresponding alkyl dihydrogen phosphates. When p-tolyl dihydrogen phosphate and ethanol were allowed to react with diethyl azodicarboxylate and triphenylphosphine, ethyl p-tolyl hydrogen phosphate and diethyl p-tolyl phosphate were obtained. On the other hand, dipyridinium p-tolyl phosphate gave ethyl p-tolyl hydrogen phosphate and di p-tolyl pyrophosphate. The reaction of alkyl N,N′-tetraethylphosphorodiamidites with carboxylic acids in the presence of diethyl azodicarboxylate resulted in the formation of corresponding carboxylic esters. When these reactions (benzoylation) were carried out with the use of optically active 2-octanol, 2-octyl benzoate was obtained with inverted configuration.
  • Masayuki Kitadani, Ken Ito, Akira Yoshikoshi
    1971 Volume 44 Issue 12 Pages 3431-3434
    Published: 1971
    Released: March 27, 2006
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    A partial synthesis of isohibaene (VI) starting with nezukol (V) has been accomplished. It involves, as the key step, the intramolecular insertion reaction of a ketocarbene generated by cuprous oxide-catalyzed decomposition of diazoketone (XI) under irradiation. It has been found that isohibaene undergoes rearrangement into a mixture of phyllocladene (XIV) and isophyllocladene (XV) by iodine catalytically.
  • Yasuo Ariyoshi, Naotake Sato
    1971 Volume 44 Issue 12 Pages 3435-3437
    Published: 1971
    Released: March 27, 2006
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    It has been found that erythro-β-hydroxy-DL-norvaline, and erythro-β-hydroxy-DL-norleucine, and threo-β-hydroxy-DL-leucine form scarcely-soluble compounds in water with α-naphthylphosphoric acid, tetrachlorophthalic acid, and chlorendic acid, respectively. On the other hand, the compounds of their diastereoisomers with the reagents were soluble in water. On the basis of these facts, β-hydroxy-DL-norvaline, β-hydroxy-DL-norleucine, and β-hydroxy-DL-leucine were successfully separated into their diastereoisomers. The configurational assignment of α-amino-β-hydroxy acids without a branched side chain on the γ-carbon atom was established by means of NMR spectroscopy.
  • Tadahiro Kato, Hideo Maeda, Mitsuaki Tsunakawa, Yoshio Kitahara
    1971 Volume 44 Issue 12 Pages 3437-3440
    Published: 1971
    Released: March 27, 2006
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    For the purpose of constructing a pinene skeleton (I), a promising intermediate for the synthesis of bergamotenes (III), the vinyl ketone (II), was synthesized from geranyl bromide (IV) by the application of Meyer’s method, followed by a Grignard reaction with vinylmagnesium bromide and subsequent oxidation. The irradiation of II in absolute ether afforded an unexpected keto ether (X) in a low yield; it was characterized by means of a deuterium-exchange reaction and physical methods. No other product except X was isolated from the photoreaction mixture of II.
  • Kiyohide Matsui, Takasi Mori, Hitosi Nozaki
    1971 Volume 44 Issue 12 Pages 3440-3443
    Published: 1971
    Released: March 27, 2006
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    The photoreactions of 11-, 12-, and 13-membered cycloalkanones (Ia, Ib, and Ic) are described. The major products are cis, trans isomers of bicyclo[n.2.0]alkan-1-ol (n=7, 8, and 9; II, III). The stereochemistry and multiplicity of the reactive species have been discussed with emphasis on the effect of the ring size. The Ib cyclododecanone is most readily susceptible to the photochemical cyclization via its S1 state, affording the cis-cyclobutanol IIb stereoselectively.
  • Shuzo Akiyama, Fumio Ogura, Masazumi Nakagawa
    1971 Volume 44 Issue 12 Pages 3443-3445
    Published: 1971
    Released: March 27, 2006
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    The formation of 9,10-dichloroanthracene by reaction of 9-acetylanthracene with phosphorus pentachloride is described. 9-Ethynylanthracene and 9-ethynyltriptycene have been prepared according to Köbrich’s method. The resulting ethynyl compounds have been converted to the corresponding di-ynes using the Eglinton’s oxidative coupling reaction.
  • Toshimasa Toda, Syoji Morimura, Eiko Mori, Hideo Horiuchi, Keisuke Mur ...
    1971 Volume 44 Issue 12 Pages 3445-3450
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    It was found that the reaction of α-amino nitriles with carbonyl compounds gave the substituted 4-oxoimidazolidines in the presence of basic catalyst. These imidazolidinones were oxidized by hydrogen peroxide: although the imidazolidinones containing an α-hydrogen at the 2- or 5-position gave no radical products, 2,2,5,5-tetrasubstituted imidazolidinones afforded new stable nitroxide radicals. By this method, stable biradicals were also prepared; but, no corresponding stable nitroxide radical was isolated by oxidation of substituted imidazolidine-4-thiones.
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