Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 47 , Issue 3
Showing 1-50 articles out of 75 articles from the selected issue
  • Tetsuhiko Yoshimura, Chie Miyake, Shosuke Imoto
    1974 Volume 47 Issue 3 Pages 515-518
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Magnetic susceptibility measurements were carried out on octacoordinated uranium(IV) complexes, such as tetrakis(acetylacetonato)uranium (IV), tetrakis(trifluoroacetylacetonato)uranium (IV), tetrakis(benzoylacetonato)uranium(IV), tetrakis(dibenzoylmethanato)uranium(IV), tetrakis(thenoyltrifluoroacetonato)uranium(IV), tetrakis(cupferronato)uranium(IV), and uranium(IV)tetrachloride, in the temperature range from room temperature to the temperature of liquid nitrogen or liquid helium. The Curie-Weiss law holds above the temperature of liquid nitrogen, with a magnetic moment of 3.5–2.92 BM. For the latter two complexes, a temperature-independent paramagnetism was observed in the low temperature range; the other complexes also seemed to show the same trend. We tried to interpret the magnetic behavior on the basis of the crystal-field model of the square antiprism structure or the dodecahedron structure of the complexes.
  • Katsuyuki Aoyagi
    1974 Volume 47 Issue 3 Pages 519-528
    Published: 1974
    Released: March 27, 2006
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    An exact solution of the equation of motion and exact expressions of the ion current in ion cyclotron resonance power absorption were obtained. Instantaneous and total power absorptions together with power absorption line shapes were derived. Ion current expressions were also derived for both nonreactive and reactive ions over the whole range of pressure. The results agreed with those obtained previously for high and low pressures with appropriate approximation. The rate constants for the disappearance of primary ions and for the formation of nonreactive secondary ions were obtained from the ion cyclotron resonance experiments. The results showed good agreement with those obtained by other methods.
  • Teikichi Sasaki
    1974 Volume 47 Issue 3 Pages 529-533
    Published: 1974
    Released: March 27, 2006
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    The yield of the trapped hydrogen atom, Ht, produced in the 6 M sulfuric acid matrix at 77 K was decreased by the presence of an electron scavenger. Based on the competition reaction kinetics, the reactivities of mobile electrons, em, with metallic and oxygen-containing ions were determined from the decrease in the Ht yield. It was found that em is scavenged most efficiently with the TeO42− ion. The relative reaction rates of em with oxyanions were generally larger than those of the corresponding eaq reactions. On the other hand, a good accordance in the reaction rates for both forms of electrons was observed in the cases of the reactions with metallic ions. An interpretation was given to the discrepancy in the observed reaction rates that em in the epithermal energy region goes over the Coulomb barrier, which is too high for eaq to pass through, and thus reacts more efficiently with anionic species than does eaq. Some unstable intermediates produced at 77 K polymerized with the solute during the thermal annealing. The ESR and optical spectra of the polymerized cadmium and molybdenum are shown, together with those of the primarily-produced species.
  • Mikio Hoshino, Masao Matsui, Masashi Imamura
    1974 Volume 47 Issue 3 Pages 534-536
    Published: 1974
    Released: March 27, 2006
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    The anion produced by the reduction of 9,9′-bixanthenylidene with sodium or potassium metal was identified with the dianion by pulse radiolysis. It appears that the dianion is twisted around the central ethylenic bond. The dianion reacts with oxygen at 100 K to produce a colored form, the spectrum of which is in accord with that of the transient species observed in the flash photolysis of 9,9′-bixanthenylidene. The colored form is expected to be produced via a twisted 9,9′-bixanthenylidene, because the oxygen is considered to remove electrons from the twisted dianion. This twisted intermediate may also participate in the photochromic or thermochromic reaction in which the same-colored form is produced.
  • Akio Furusaki, Nobuyuki Hamanaka, Takeshi Matsumoto
    1974 Volume 47 Issue 3 Pages 537-544
    Published: 1974
    Released: March 27, 2006
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    The crystal structure of the title compound has been determined from three-dimensional data collected on an automatic, four-circle diffractometer. The racemic crystals are triclinic, with two molecules in a unit cell of these dimensions; a=10.502, b=11.706, c=7.488 Å, α=71°33′, β=91°46′, and γ=116°22′. The space group is P\bar1. The structure was solved by the symbolic addition method and was then refined by the block-diagonalmatrix least-squares method, with isotropic temperature factors for the hydrogen atoms and with anisotropic ones for the others. The final R value was 6.7%. The length of the C–C single bond opposite to the double bond in the cyclohexene ring is only 1.34±0.01 Å. This apparent remarkable shortening can be well explained on the assumption that the two atoms concerned vibrate vigorously with parallel and antiparallel harmonic components perpendicular to the plane of the ring. It is shown that, if the root-mean-square amplitudes of the former components are taken to be equal to that of the thermal vibration of the carbon atom adjacent to one of the two atoms, the above C–C distance, corrected for these antiparallel motions, becomes quite reasonable: 1.60 Å.
  • Shunsuke Kuribayashi
    1974 Volume 47 Issue 3 Pages 545-547
    Published: 1974
    Released: March 27, 2006
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    The crystal structure of meso-(2S,4s,6R)-2,4,6-heptanetriol has been determined by means of X-ray methods. The crystal belongs to monoclinic system (space group Ic), with four molecules in a unit cell with dimensions of a=8.133, b=9.374, c=11.248 Å, and β=93.24°. The structure was solved by three-dimensional Patterson and trial-and-error methods. The final R factor was 0.076. The molecule has the GTT\barG conformation, and all of the OH groups are linked together by intermolecular hydrogen bonds.
  • Kohji Tadasa, Naomi Imai, Tetsuo Inaba
    1974 Volume 47 Issue 3 Pages 548-552
    Published: 1974
    Released: March 27, 2006
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    The pyrolysis of formaldehyde was investigated in the presence of nitric oxide at 500 °C. The kinetics of the reaction suggests that the pyrolysis proceeds by means of a mechanism which is initiated by this reaction:
    NO+CH_2O→HNO+CHO
    and which involves this reaction:
    HNO+HNO→N_2+2OH
    as one of the chain-carrying steps.
  • Seiichi Kondo, Masa-aki Muroya, Kenzo Fujii
    1974 Volume 47 Issue 3 Pages 553-556
    Published: 1974
    Released: March 27, 2006
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    The thermal behavior of the silanol of silica gel has been studied by quantitative infrared spectroscopy. Transparent and glass-like plates of silica gel of high purity, after they had been heat-treated at various temperatures below 680 °C, were used for the measurement of OH stretching vibrations ranging from 3100 to 3800 cm−1. These absorption bands were analysed into the several component bands by the simulation method using a Dupont Co. Curve Resolver. The intensity of these bands in area were proportional to the OH concentrations as measured by the thermal method. Each component band disappeared at a temperature which was roughly equal to that obtained from the dielectric and conductivity measurements. From these results, assignment was attempted on the basis of these bands.
  • Katsutoshi Ohkubo
    1974 Volume 47 Issue 3 Pages 557-560
    Published: 1974
    Released: March 27, 2006
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    UV spectroscopic and semiempirical SCFMO investigations have been performed on the partially-occupied (formally unoccupied) d-orbitals participating in the activation of the ground state, 3Σg–O2, with special attention being given to the catalytic activities of onium compounds. The order of the red shifts of the (pz)2→(pz)(d) transition of the onium compounds in an oxygen atmosphere is in satisfactory accordance with those of the magnitude, of the partial occupancy of the d-orbitals and of the catalytic activities of the onium compounds in hydrocarbon oxidations. The dxz (or dyz) and dx2y2 orbitals are most favorably disposed for the interactions between the Group VI and V onium compounds and the (1πg)-orbital of the 3Σg–O2 respectively. The partial occupation of the formally unoccupied d-orbitals results from the d-π delocalization between the onium central atom and the neighboring atoms of substituents and the counter-anion.
  • Hirokazu Miyoshi
    1974 Volume 47 Issue 3 Pages 561-565
    Published: 1974
    Released: March 27, 2006
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    The magnetic susceptibilities of manganese(II) phthalocyanine (PcMn) have been measured in the paramagnetic region between 13.8 and 280 K. The deviation from the Curie-Weiss law was found at a moderately high temperature (about 70 K), and the Weiss constant was obtained as 23 K. Comparing the ratio of Tc to θ (0.37) with that of the 2- or 3-dimensional lattice, the data were analysed on the basis of the ferro-magnetic linearchain model. The magnitude of the intra-chain interaction (J) was deduced as 5.64k by comparison with Fisher’s classical form of the theory of the ferromagnetic Heisenberg chain. We have also measured the magnetic susceptibilities of cobalt(II) phthalocyanine (PcCo) and of copper(II) phthalocyanine (PcCu), which are isomorphous with manganese(II) phthalocyanine, from 1.8 to 77 K. In PcCo, a broad maximum has been observed, and the data were analysed in terms of the theory of the antiferromagnetic Ising-chain model. On the other hand, PcCu obeyed the Curie law down to 1.8 K. A qualitative explanation of the exchange interactions in PcMn, PcCo, and PcCu was presented on the basis of their electronic states.
  • Nobuo Takenaka, Kiyoshi Arakawa
    1974 Volume 47 Issue 3 Pages 566-570
    Published: 1974
    Released: March 27, 2006
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    Ultrasonic velocity and absorption were measured for binary mixtures of water and ethers (1,2-dimethoxyethane, bis(2-ethoxyethyl)ether, bis (2-methoxyethyl)ether, ethylether, diethoxymethane, 1,1-diethoxyethane and 1,2-diethoxyethane) in the frequency range 15–45 MHz at 10–30 °C. Vibrational relaxation was observed in the pure liquid of 1,2-dimethoxyethane. For each solution of 1,2-dimethoxyethane and bis(2-methoxyethyl)ether, the maximum absorption at the intermediate composition was ascribed to the formation of dihydrate and trihydrate, respectively. The difference between the behavior of ethyl group in water and that of methyl group was discussed from the absorption data.
  • Ryuichiro Ohnishi, Kozo Tanabe, Shinsuke Morikawa, Tadao Nishizaki
    1974 Volume 47 Issue 3 Pages 571-574
    Published: 1974
    Released: March 27, 2006
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    The isomerization of 2-pinene (I) and 2(10)-pinene (II) in the liquid phase has been studied at 50 °C over solid acid catalysts such as silica–alumina, aluminum phosphate, nickel sulfate and zinc sulfide which have different acid strengths. The primary reaction products were camphene (III), 1,7,7-trimethyl-tricyclo[2.2.1.02,6]heptane (IV) and p-mentha-1,8-diene (VI). The catalytic activities increased with increasing acid strength and acid amount of the catalysts. The selectivities for the formation of III+IV and VI from I were about 90 and 10% respectively over NiSO4, but about 10 and 70% respectively over SiO2–Al2O3 and AlPO4. Those for the formation of I, III+IV and VI from II also depended on the acid strength. In the isomerization of VI, p-mentha-1,4(8)-diene (VII) was formed predominantly over NiSO4 and p-cymene (IX) over SiO2–Al2O3. From these results together with those of the isomerizations of III and IV, a reaction mechanism is proposed which consists of two parallel reactions proceeding via a common intermediate between I and II: one which gives monocyclic terpenes and the other bi- and tricyclic terpenes.
  • A. C. Herd, Takaharu Onishi, Kenzi Tamaru
    1974 Volume 47 Issue 3 Pages 575-578
    Published: 1974
    Released: March 27, 2006
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    The mechanism of methanol oxidation on zinc oxide was studied by quantitatively observing the dynamic behaviour of the surface species during the course of the reaction. It was concluded that the mechanism was similar to that of the decomposition reaction, with an additional step, the oxidation of the carbon monoxide formed. As a key step in the oxidation of methanol, the decomposition of adsorbed methoxide groups in the presence of oxygen at temperatures between 140 and 180 °C has been studied by infrared spectroscopy. The methoxide groups decompose to formate ions until a maximum surface concentration is reached. The rate of decomposition at first increases with methoxide concentration, then decreases as the surface coverage approaches saturation. The observed kinetics can be explained by a mechanism which postulates that negatively charged surface species repel electrons from the surface of the zinc oxide, thus inhibiting decomposition of the methoxide groups.
  • Katsutoshi Ohkubo, Kohji Tsuchihashi, Hiroyuki Sakamoto
    1974 Volume 47 Issue 3 Pages 579-582
    Published: 1974
    Released: March 27, 2006
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    A new technique using the polynomials approximation and the trapezoidal average method, has been proposed for estimating kinetic rate constants. It is implemented by minimizing the error of the concentration (of a product) obtained from the polynomial-approximated least square-error analysis of the observed concentrations during the initial reaction stage relative to that obtained theoretically from the trapezoidal average of the calculated concentration (of a product) on the basis of the law of mass action. The technique is useful for easily and exactly estimating the rate constants in systems of linear or nonlinear differential equations. A kinetic model, A→ B\ ightleftarrowsC, was used to illustrate and develop the present technique.
  • Yozo Chatani, Tadafumi Yamauchi, Yasuhiko Miyake
    1974 Volume 47 Issue 3 Pages 583-588
    Published: 1974
    Released: March 27, 2006
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    The crystal structure of the cyclic tetramer of formaldehyde, 1,3,5,7-tetroxocane, has been determined by the X-ray diffraction method. The unit cell is monoclinic, with a=11.455, b=4.160, c=12.232 Å, and β=108.4°. The space group is C2/c, and there are four molecules per unit cell. The structure was solved by using a molecular transform method and was refined by the block-diagonal least-squares method to a final R factor of 0.051, using 728 reflections measured with an automated four-circle diffractometer. The molecules in the crystal are of the so-called crown form, with an approximate C4v symmetry but an exact C2 symmetry. The torsion angles about the four independent C–O bonds appear in two distinguishable values: two bonds with 83.7 and −83.6°, and the other two bonds with 93.6 and −94.1°. The average C–O bond length is 1.403 Å, while the average C–O–C and O–C–O bond angles are 116.6 and 113.8° respectively. The deformation from a regular crown form by taking the two distinguishable torsion angles and the increase in bond angles is favorable to compensating for the intramolecular H···H repulsions; the close H···H distances in the deformed crown form are 2.16 and 2.20 Å.
  • Masahiro Kondo, Isao Ando, Riichirô Chûjô, Atsuo Nis ...
    1974 Volume 47 Issue 3 Pages 589-592
    Published: 1974
    Released: March 27, 2006
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    The proton NMR spectra of some partially deuterated n-pentanes were observed under both proton-deuteron (H–D) spin-coupled and -decoupled conditions. With using the spectrum-simulation method, it was confirmed experimentally that the chemical shift of the CH2(3) protons appears at a higher field than that of the CH2(2) protons.
  • Norio Nishimura, Tatsuo Higashiyama
    1974 Volume 47 Issue 3 Pages 593-596
    Published: 1974
    Released: March 27, 2006
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    Phase diagrams were constructed for the equilibria of the AgI–NaI–H2O system at temperatures 0–70 °C. A compound AgI·NaI·3H2O was isolated, and the compound was found by means of X-ray analysis to belong to the orthorhombic system with cell constants a=8.78, b=33.5, and c=6.48 Å.
  • Masamoto Iwaizumi, Shozo Kubota, Taro Isobe
    1974 Volume 47 Issue 3 Pages 597-599
    Published: 1974
    Released: March 27, 2006
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    Nitric oxide adsorbed on silica gel was investigated by ESR. It was found that there are at least two adsorption sites for nitric oxide; one of them is on the silica gel which has been pretreated at low temperatures (below ca. 500 °C) (Site L), while the other is predominantly on the silica gel which has been pretreated at high temperatures (above ca, 500 °C) (Site H). The crystal-field splitting of the Πx* and ΠY* states, which are originally degenerate, was determined to be 0.26 eV for the nitric oxide adsorbed on Site L and 0.52 eV for the nitric oxide on Site H. The temperature dependence of the ESR spectrum was also examined, and the average crystal field acting on nitric oxide was found to decrease with an increase in the temperature.
  • Seiichi Kurihara, Kazuo Fueki, Takashi Mukaibo
    1974 Volume 47 Issue 3 Pages 600-603
    Published: 1974
    Released: March 27, 2006
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    A new method for obtaining the self-diffusion coefficients of A in the AY–BY solid solution has been proposed. In this method, the tracer diffusion of A* and the interdiffusion between AY and BY are carried out simultaneously, and the self-diffusion coefficients are determined as a function of composition over the whole range of composition in a similar way as the Boltzmann-Matano analysis. Since this method employs a diffusion couple consisting of single crystals of AY and BY, one can avoid troubles and errors due to segregation and/or phase separation which are often encountered in experiments using solid solutions as specimens. In order to confirm the validity of the proposed method, Dcl* in the TlCl–TlBr system and DAg* and DNa* in the AgBr–NaBr system have been determined at 400 °C by this method and compared with the results obtained by the conventional method. A good agreement has been found between them.
  • Satoru Matsumoto, Saburo Nagakura, Yasuyuki Shimozato, Hisaharu Hayash ...
    1974 Volume 47 Issue 3 Pages 604-610
    Published: 1974
    Released: March 27, 2006
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    Triplet-triplet absorption, phosphorescence, and ESR spectra have been measured on the 1,3,5-tricyanobenzene complexes with toluene, mesitylene, durene, and hexamethylbenzene. Four triplet-triplet absorption bands were commonly observed in the wave number region of 10000–30000 cm−1 for all the complexes. The observed phosphorescence and T-T absorption spectra could be understood systematically by considering the interaction among zero-order charge-transfer triplet states and zero-order locally (within the acceptor) excited triplet states. From an analysis of the zero-field splitting values obtained from the observed ESR spectra, the contribution of the zero-order charge-transfer triplet state to the lowest triplet state was determined to be 76,65,25, and 9% for the 1,3,5-tricyanobenzene complexes with hexamethylbenzene, durene, mesitylene, and toluene, respectively. From the consideration on the results obtained for various polycyanobenzene complexes, the phosphorescence lifetime was found to decrease remarkably for the complexes with the charge-transfer character higher than 50% in their lowest triplet states.
  • Kiwamu Yamaoka, Mineo Takatsuki, Kunio Yaguchi, Masaji Miura
    1974 Volume 47 Issue 3 Pages 611-617
    Published: 1974
    Released: March 27, 2006
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    The interaction of crystal violet with sodium polyphosphate in aqueous solutions at neutral pH has been investigated by means of visible absorption spectroscopy and electric conductivity. The mixing ratio of polymer residue to dye was varied from 0.1 to 10000. The metachromasy band at 506 nm was found to fully develop between 3 and 10, whereas conductometric titration showed that crystal violet saturates the polymer site. Emphasis was placed on the effect of the polymer chain length on the metachromasy band. To study this effect, 17 fractionated and 13 refractionated polymer samples with degrees of polymerization extending from 4 to 300 were utilized. A critical range of the degree of polymerization from the metachromasy band exists between 7 and 20. The effect of small ions on metachromasy was also studied using sodium phosphates. An increase in Na+ ions tends to suppress the metachromasy band. This effect is more pronounced with shorter polymer lengths. In order to explain the observed metachromasy phenomena, two mechanisms were postulated; one attributes metachromasy to the flexibility of the polymer backbone when dye is present, and the other deals with specific interaction of dye and polymer site.
  • Taro Koshii, Eiji Arie, Masahiko Nakamura, Hiroaki Takahashi, Keniti H ...
    1974 Volume 47 Issue 3 Pages 618-622
    Published: 1974
    Released: March 27, 2006
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    The dielectric constants and losses of 1-propanol and its mixtures with benzene, chlorobenzene, 1,4-dioxane or pyridine, and 1-butanol and its mixtures with benzene or pyridine have been measured in the frequency range of 0.35–2.1 GHz at 25.0 °C. Concentrations of alcohols are 1–0.6 mol fraction of the mixtures. Densities and refractive indices have also been determined. The dielectric data were used to calculate the relaxation times of the alcohols. The Cole-Cole plots for these systems showed Debye-type semicircles in lower frequencies where the principal relaxation of alcohols dominates. Deviations from the semicircle, however, have been observed in the region of upper frequencies, where the second dispersion of alcohol, the dispersion of solvent itself and of hydrogen-bonded species between alcohol and solvent may occur. The principal relaxation times of alcohols calculated from the data of lower frequencies change with concentration in two different manners by solvents, and this difference is due to whether the solvent has hydrogen-bonding capacity or not, and does not depend upon the dielectric constant and/or the polarity of the solvent.
  • Taro Koshii, Eiji Arie, Masahiko Nakamura, Hiroaki Takahashi, Keniti H ...
    1974 Volume 47 Issue 3 Pages 623-626
    Published: 1974
    Released: March 27, 2006
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    The dielectric constants and losses of 2-propanol and its mixtures with benzene, chlorobenzene, 1,4-dioxane or pyridine and 2-methylpropanol or 2-butanol and their mixtures with benzene or pyridine have been measured in the frequency range of 0.35–2.1 GHz at 25.0 °C. Concentrations of alcohols are 1–0.6 mol fractions of the mixtures. The principal relaxation times and the Kirkwood correlation factor g were evaluated. Variation of the principal relaxation times against the concentrations of these branched alcohol mixtures is not much different from that of normal alcohol mixtures. The g factor decreases almost monotonously with increasing amount of solvent exception being found in case for propanol–benzene mixtures.
  • Iwao Watanabe, Yu Yokoyama, Shigero Ikeda
    1974 Volume 47 Issue 3 Pages 627-630
    Published: 1974
    Released: March 27, 2006
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    The first and the second bands of the photoelectron spectra of acetic, propionic, and isobutyric acids were recorded, and the vibrational structures in the spectra were studied by comparing with the results of formic acid. The first band exhibits a νc=o, a δOH, and a ρCOOH vibrational progression, and this implies that an oxygen lone pair orbital, from which the first band of the spectra originates, contributes not only to a C=O bonding and the bonding between carbonyl oxygen and hydroxyl hydrogen, but to the settling of carboxyl group in the molecular plane. The second band exhibits a νc=o, a νc-o vibrational progression with very high frequency for the νc=o as observed in the case of formic acid. Thus the vibrational features of the second band are consistent with the ionization of an antisymmetric π orbital localized mainly on carbonyl and hydroxyl oxygen atoms. Since the 0-0 vibrational transitions for the second ionization are out of the Franck-Condon region, the second adiabatic ionization potential was estimated by comparing the vibrational fine structures of the spectra with that of formic acid. The second adiabatic ionization potential of acetic acid so determined is 11.63 eV.
  • Mitsuo Kitano, Kozo Kuchitsu
    1974 Volume 47 Issue 3 Pages 631-634
    Published: 1974
    Released: March 27, 2006
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    The bond distances (rg) and angles (ra) in N-methylformamide HCONHCH3 have been determined by gas electron diffraction as follows: N–C (methyl)=1.459±0.006 Å, C(carbonyl)–N=1.366±0.008 Å, C=O=1.219±0.005 Å, C–H(methyl)=1.114±0.025 Å, <N–C=O=124.6±0.5° and <C–N–C=121.4±0.9°, where uncertainties represent estimated limits of experimental error. Systematic trends are observed among the skeletal structures of formamide, acetamide, N-methylformamide and N-methylacetamide. A conformer with the C(carbonyl)–H and N–C(methyl) bonds trans to each other is found to be dominant in the gas phase. The presence of a small fraction of the cis conformer is suggested, but the experimental evidence is not conclusive.
  • Mitsuo Hara, Shin Suzuki
    1974 Volume 47 Issue 3 Pages 635-638
    Published: 1974
    Released: March 27, 2006
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    The behavior of Am(III), Am(V), and Am(VI) in column chromatography with bis(2-ethylhexyl)phosphoric acid(HDEHP) used as the extractant were investigated in comparison with that of Np(IV), Np(V), and Np(VI). When the solution of Am(VI) was submitted to the column chromatography, it was found that Am(VI) was rapidly reduced to Am(V) and partially to Am(III) by HDEHP, irrespective of the conditions, such as the flow rate, the acidity, and the composition and temperature of the influent. The optimum conditions for the separation of Am(V) and Am(III) and for the preparation of the Am(V) solution were established by utilizing the difference in the adsorbability on the column bed between Am(III) and Am(V). When a freshly-prepared Am(V) solution was submitted to column chromatography, it was found that Am(V) was also reduced to Am(III) as well as Am(VI) by HDEHP. The percentage of the Am(V) fraction eluted strongly depended on the conditions in the column chromatography, but it was found to be constant within the limits of experimental error under definite conditions as long as the same column was used. This fact was applied to the determination of the Am(V) content in the mixed solution of Am(III) and Am(V). The content of Am(V) decreased slowly in the nitrate, acetate, sulfate, and perchlorate solutions at lower temperatures, but it rapidly decreased in the chloride, iodide, sulfite, and hydrogen peroxide solutions even at 0 °C. The content of Am(V) decreased more rapidly at higher temperatures, and the kinetic analysis showed that the reduction of Am(V) apparently followed the first-order kinetics in the acetate solutions.
  • Hiroshi Yokoi
    1974 Volume 47 Issue 3 Pages 639-644
    Published: 1974
    Released: March 27, 2006
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    The molecular g values of several bis(amino acidato) copper(II) complexes in crystals, whose crystal structures with two molecules per unit cell are known, have been estimated from the crystal g values by considering the effect of the spin-exchange interaction between the dissimilar copper(II) ions. All the crystal g values have been determined here from the powder K-band ESR spectra. Many other complexes with unknown crystal structures have also been dealt with in a similar way. The results have indicated that most of the complexes probably have a tetragonal or nearly tetragonal copper (II) ion environment in crystals, and a tendency for the estimated g⁄⁄ value to decrease with an increase in the energy of the visible absorption peak in crystals have been noted. A discussion about the correlation between an axial molecular g tensor and the two copper-ligand bond lengths of Cu–O and Cu–N has been given.
  • Shinnichiro Suzuki, Masayoshi Nakahara, Ken-ichi Watanabe
    1974 Volume 47 Issue 3 Pages 645-647
    Published: 1974
    Released: March 27, 2006
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    On treatment of bis(2-pyridinecarbonitrile)copper(II) chloride with various amines in methanol, the alkoxylation of the nitrile group in the complex took place; in some cases, the alkoxylation and the ligand substitution of the complex occurred at the same time. The reaction products were classified into three types depending on the amines used; two of the types consisted of new complexes. The complexes of CuCl2(MeOpy)(Amine) (MeOpy: O-methylpyridine-2-carboximidate), were obtained on the addition of ammonia, methylamine, dimethylamine, ethylamine, benzylamine, or piperidine to a methanol solution of bis(2-pyridinecarbonitrile)copper(II) chloride. On the other hand, the addition of trimethylamine, diethylamine, or triethylamine afforded the complex of CuCl2(MeOpy)2. These types of complexes were not obtained by the use of aniline or pyridine; but the previously known complex, CuCl2(MeOpy), was obatined in this case. It has been assumed that the formation of the three types of complexes is essentially the result of both the basicities and the steric factors of the amines.
  • Norifumi Yoshida, Akira Matsumoto, Jiro Shiokawa
    1974 Volume 47 Issue 3 Pages 648-651
    Published: 1974
    Released: March 27, 2006
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    N,N′-Bis(1-acetonylethylidene)ethylenediamine(AEH2) complexes were prepared by the reaction of hydrous rare earth perchlorates with AEH2 in methanol. Elemental analysis, X-ray powder diffraction analysis, pH titration, IR and luminescence spectrometries indicated that the complexes of the lighter rare earths were Ln(AEH2)4(ClO4)3, where Ln are La, Pr, Nd, and Sm, while the complexes of the heavier rare earths were hydroxocomplexes, Ln(AEH2)2(ClO4)2(OH)·H2O, where Ln are Gd, Dy, and Er. Anhydrous gadolinium perchlorate was reacted with AEH2 in methanol under anhydrous conditions to give Gd(AEH2)4(ClO4)3. It was possible that a water molecule played an important role in the complexation of rare earth perchlorates with AEH2 in methanol. The formation of the hydroxocomplexes with AEH2 was related to the low coordinating ability of the perchlorate ion and to the charge densities of the rare earth ions as well as to the basicity of AEH2.
  • Hisaya Oki, Meiji Yasuoka, Ryokichi Tsuchiya
    1974 Volume 47 Issue 3 Pages 652-655
    Published: 1974
    Released: March 27, 2006
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    The thermal decomposition of [Cr(NH3)6](SCN)3, [Cr(NCS)(NH3)5](SCN)2 and cis-[Cr(NCS)2(NH3)4]SCN in solid state was studied by isothermal as well as continuous temperature-rise methods. Under isothermal heating at 140°C, [Cr(NH3)6](SCN)3 changed stepwise to cis, trans-[Cr(NCS)3(NH3)3] through trans-[Cr(NCS)2(NH3)4]SCN, [Cr(NCS)(NH3)5](SCN)2 turning to the cis-trans complex over the trans complex in the same manner as [Cr(NH3)6](SCN)3. Under the continuous temperature-rise, [Cr(NH3)6](SCN)3, [Cr(NCS)(NH3)5](SCN)2 as well as trans-[Cr(NCS)2(NH3)4]SCN were found to be directly converted into cis,trans-[Cr(NCS)3(NH3)3].
  • Eiichi Miki, Kunihiko Mizumachi, Tatsujiro Ishimori, Hisateru Okuno
    1974 Volume 47 Issue 3 Pages 656-659
    Published: 1974
    Released: March 27, 2006
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    The 15NO-complexes for trans-[PtCl(NH3)4(NO)]Cl2, trans-K2[PtCl(NO2)4(NO)] and M2[PtX5(NO)] (M=K and Cs, X=Cl and Br) were prepared. The effect of 15N-substitution on infrared spectra indicated that the weak absorption band at ca. 290 cm−1 is assigned to the Pt-(NO) stretching vibration and the absorptoin band in the region 530–570 cm−1 to the Pt-(NO) bending vibration.
  • Ryokichi Tsuchiya, Masaaki Yonemura, Akira Uehara, Eishin Kyuno
    1974 Volume 47 Issue 3 Pages 660-664
    Published: 1974
    Released: March 27, 2006
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    The thermal decomposition of [Ni(N2H4)6]X2 (X=Cl, Br, I) in solid phase was investigated by means of derivatography and IR spectral measurement. It was found from the derivatography that the decomposition of the chloride and bromide proceeded via tris-, bis-, and mono-hydrazine complexes as metastable reaction intermediates, while tetra-hydrazine complex was produced in the decomposition of the iodide instead of the tris-one which appeared in the chloride and bromide. IR spectra showed that, although the hexa-hydrazine complex as a starting material contains only unidentate hydrazine coordinated by either one of terminal nitrogen atoms, all the reaction intermediates have bidentate one bridging between two nickel ions. In particular, it was of much interest that the decomposition of these hydrazine complexes was remarkably exothermic, a part of the reasons being discussed.
  • Shigeru Baba, Tetsuya Ogura, Shinichi Kawaguchi
    1974 Volume 47 Issue 3 Pages 665-668
    Published: 1974
    Released: March 27, 2006
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    Bis (acetylacetonato)palladium (II) reacts with triphenylphosphine and nitrogen bases such as pyridine, diethylamine, and N-methylbenzylamine to transform one of the chelating ligands into the carbon-bonded state. The product complexes of the type Pd(acac)2L have been isolated in high yields and characterized by IR and NMR spectra. Several reactions of Pd(acac)2PPh3 and Pd(acac)2py were also examined.
  • Hayami Yoneda, Yoshiaki Nakashima
    1974 Volume 47 Issue 3 Pages 669-672
    Published: 1974
    Released: March 27, 2006
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    The proton magnetic resonance spectra have been measured in dimethylsulfoxide on some cobalt(III) complexes of the type [CoX(NH3)5]. Ammine protons show two peaks, except in a complex with X=NO2. The major peak, due to cis NH3, appears downfields and the minor one, due to trans NH3, upfields as compared with the shift in [Co(NH3)6]3+. In the case of X=CN, the shift pattern is reversed. For [Co(NO2)(NH3)5]2+, the spectrum is a single peak. This chemical shift behavior is explained by a simple model based on Ramsay’s theory for chemical shift. It is concluded that the behavior arises primarily from paramagnetic anisotropy of the central cobalt (III) ion. The model used in this work is shown to be applicable also to the assignment of the PMR spectra for complexes of the types cis-[CoX2(NH3)4] and cis-[CoX2(en)2].
  • Akira Matsumoto, Tetsuji Ohata, Masayoshi Oiwa
    1974 Volume 47 Issue 3 Pages 673-676
    Published: 1974
    Released: March 27, 2006
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    The radical polymerization of triallyl citrate was carried out at 60 °C, benzoyl peroxide being used as the initiator and benzene as the solvent; here it has been considered kinetically in terms of cyclopolymerization. Thus, the kinetic equations for the polymerization of the triallyl ester were first derived by an extension of the kinetic treatment for the cyclopolymerization of the diallyl ester. Next, they were applied to the polymerization of triallyl citrate. In consequence, the following results were obtained: (i) the rate of polymerization, Rp, was not proportional to either the square root or first power of the initiator concentration, [I]; rather, Rp/[I]1⁄2 and [I]1⁄2had a linear relationship, (ii) the relation between the rate of polymerization over the degree of polymerization, Rp/\barPn,o, and the monomer concentration, [M], was also linear, and (iii) the ratio of the unimolecular cyclization reaction to the bimolecular propagation reaction of the uncyclized radical, Kc, was estimated to be 4.5 mol/1 from the dependence of the residual unsaturation on the monomer concentration.
  • Y\={u}ji Yanagida, Hideo Shigesato, Masakatsu Nomura, Sh\={o}ichi Kikk ...
    1974 Volume 47 Issue 3 Pages 677-680
    Published: 1974
    Released: March 27, 2006
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    The reaction of bromine with both trans-5,6-dichloro-2-norbornene (I) and exo-cis-5,6-dichloro-2-norbornene (III) in an acetic acid solution gave trans-adducts in a 100% yield, while the bromination of endo-cisr-5,6-dichloronorbornene (II) afforded the endo-cis adduct in a ca. 100% yield. The latter observation was explained in terms of a sterical inhibition of the bromide ion’s attack in the endo-direction by the two endo-chloro substituents. In the CCl4 solution, however the reaction of I with bromine afforded the exo-cis adduct in a 64% yield, together with the trans-adduct (36% yield). Then, the reaction of I with bromine was carried out in several other solvents (CH3OH, Cl(CH2)2Cl, CH3CO2C2H5, and CCl4). As the polarity of the solvents (the ET values are used here as a measure of the solvents’ polarity) decreased, the formation of the exo-cis adduct became progressively more predominant, while the addition of bromide salt retarded the formation of the exo-cis adduct. Such results and the kinetic studies suggested that the exo-cis adduct was formed through the carbonium bromide ion-pair mechanism. The stereoisomers obtained in this study were assigned on the basis of the NMR spectra.
  • Tetsuo Nozoe, Toyonobu Asao, Masaji Oda
    1974 Volume 47 Issue 3 Pages 681-686
    Published: 1974
    Released: March 27, 2006
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    The bromination, chlorination, and nitration of 1,3-disubstituted 2-hydroxyazulenes were investigated. Bromination by bromine or NBS afforded 1-bromoazulan-2-one derivatives as kinetically-controlled products and 6-bromo-2-hydroxyazulene derivatives as thermodynamically-controlled products. Ghlorination by NCS gave 1-chloroazulan-2-one derivatives, while that by chlorine afforded further chlorine addition products. Nitration afforded a mixture of 1-nitroazulan-2-one and 6-nitro-2-hydroxyazulene derivatives. The ultraviolet, infrared, and NMR spectra of the products were discussed.
  • Hiroshi Suginome, Tsutomu Uchida
    1974 Volume 47 Issue 3 Pages 687-691
    Published: 1974
    Released: March 27, 2006
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    The photolysis of androsterone oxime and 13α-androsterone oxime affords isomeric lactams with and without the original configuration of the C-13 substituent of the starting oxime, although there were poor yields and no products due to photo-Beckmann fission. The formation of an epimeric pair of lactams from an oxime is at variance with our previous results on the photolysis of 5α- and 5β-cholestan-6-one oximes, in which the stereochemical integrity of the terminus of the migrating carbon in the photo-Beckmann rearrangement was observed. The implication of the present results for the migration step of the photo-Beckmann rearrangement is discussed.
  • Sakae Uemura, Akira Onoe, Masaya Okano
    1974 Volume 47 Issue 3 Pages 692-697
    Published: 1974
    Released: March 27, 2006
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    Antimony(V) chloride was revealed to be a good reagent for the cis-chlorination of simple olefins in chlorinated hydrocarbon solvents, such as 1,2-dichloroethane, dichloromethane, chloroform, and carbon tetrachloride. The higher the reaction temperature or the solvent polarity was, the higher the selectivity for cis-chlorination became. From 1,3-butadiene, cis-1,4-dichloro-2-butene was formed together with the trans-1,4- and 1,2-dichloro isomers. In the cases of cyclopentene and norbornene, the trans-1,2-dichloride and other various dichlorides were obtained without any formation of the cis-1,2-isomer. Probable mechanisms for this chlorination are briefly discussed.
  • Hiroshi Sugano, Hayao Abe, Muneji Miyoshi, Tetsuo Kato, Nobuo Izumiya
    1974 Volume 47 Issue 3 Pages 698-703
    Published: 1974
    Released: March 27, 2006
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    Two analogs of gramicidin S, cyclo(–Val–Orn–Leu–D-Phe–Pro–Val–Orn–MeLeu–D-Phe–Pro–), i.e., [3-N-Methylleucine]–gramicidin S, and cyclo(–Val–Orn–MeLeu–D-Phe–Pro–Val–Orn–MeLeu–D-Phe–Pro–), i.e., [3,3′-di-N-Methylleucine]–gramicidin S, were prepared in an attempt to investigate the contribution of the NH group of the leucine residue with regard to antibacterial activity. These analogs were almost as active as gramicidin S in the antibacterial test in reaction to microorganisms. The optical rotatory dispersions of these two analogs and of gramicidin S were measured in solvents of ethanol and 8 M aqueous urea. These studies suggested that both of the analogs containing N-methylleucine have a molecular conformation very similar to that of gramicidin S, and that the NH group of the leucine residues is not necessary for stabilizing the conformation in order to exhibit the biological properties.
  • Akira Sera, Chisako Yamagami, Kazuhiro Maruyama
    1974 Volume 47 Issue 3 Pages 704-707
    Published: 1974
    Released: March 27, 2006
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    The effect of pressure on the formolysis of 1-(P-substituted benzyl) ethyl tosylates was investigated, and the activation volumes, ΔVo\ eweq were estimated. The apparent values of activation volume were found to correlate nicely with σ*. Because the present substrates were believed to be formolyzed through two separate processes, anchimerically assisted (kΔ) and unassisted (ks), the apparent values of activation volume were partitioned into the corresponding activation volumes, ΔVΔ\ eweq and ΔVs\ eweq. The dependence of ΔVΔ\ eweq and ΔVs\ eweq on the substituents was examined, and the correlation between the mechanisms of solvolysis and ΔVΔ\ eweq and ΔVs\ eweq was discussed.
  • Mamoru Imanari, Masahiro Kohno, Muneki Ohuchi, Kazuhiko Ishizu
    1974 Volume 47 Issue 3 Pages 708-711
    Published: 1974
    Released: March 27, 2006
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    The natural-abundance 13C NMR spectra of the ortho- or the para-halobiphenyls were obtained by the pulse Fourier transform NMR (FT-NMR). For the para-derivatives, the observed chemical shifts of the C1 C2, and C3-positions gave an excellent linear dependence on the electronegativity of the substituents. The dependence for the C4-position, which showed a deviation from the linear plot, may be due to the heavy atom effects. The additivity of the chemical shifts holds also for the ortho-derivatives except for the cases of the bridgehead carbons, the C1 and C1′-positions. In particular, the observed chemical shifts of the C2, C3, and C4 positions for 2,2′,6,6′-tetrachlorobiphenyl showed a good agreement with the predicted values, whereas a large discrepancy can be seen between the observed and the assumed values for the C1 and C1′ positions. The effects on the chemical shifts due to the steric hindrance are discussed by comparison with the results of the hindered alkylbiphenyls. The temperature dependence of the spin-lattice relaxation time was investigated for 4,4′- and 2,2′-dichlorobiphenyls. The activation energies of the molecular reorientation are negligibly small at the C1 and C4-positions for the para-derivative, but the ortho-derivatives have higher values at these positions, indicating anisotropy for the molecular motion.
  • Kazuhiro Maruyama, Mamoru Taniuchi, Shinzaburo Oka
    1974 Volume 47 Issue 3 Pages 712-714
    Published: 1974
    Released: March 27, 2006
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    The thermal decomposition of di-t-butyl peroxide in aliphatic aldehydes has been carefully examined. n-Aldehydes and β-substituted aldehyde gave appreciable amounts of sec-alcohols in the reactions, sec-Alcohol arose from the addition of the alkyl radical to the carbonyl group of aldehyde. α-Substituted aldehydes, however, did not give sec-alcohol, but instead gave considerable amounts of enol ether-aldehydes and dialdehydes. The addition of the alkyl radical to the carbonyl group and the decarbonylation of aldehydes were influenced remarkably by the structures of the aldehydes.
  • Tadashi Sato, Eigoro Murayama
    1974 Volume 47 Issue 3 Pages 715-719
    Published: 1974
    Released: March 27, 2006
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    The unsensitized photooxidation of (+)-lmionene (1), 1,2-dimethylcyclohexene (2) and endo-dicyclopentadiene (3) were carried out with Pyrex-filtered light. The singlet-oxygen oxidation was found to occur concurrently with the radical oxidation to the extent of 41% with 1 and 66% with 2, but not at all with 3. A reaction path via a complex was proposed.
  • Yoshikazu Isowa, Hideaki Kurita
    1974 Volume 47 Issue 3 Pages 720-722
    Published: 1974
    Released: March 27, 2006
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    The reactions of N-tosyl-O-2,4,6-trimethylbenzylhydroxylamine with primary alkyl halides yielded the protected hydroxylamines. The simultaneous cleavage of N-tosyl- and O-2,4,6-trimethylbenzyl groups with hydrogen bromide in acetic acid gave the corresponding N-monoalkylated hydroxylamines such as N-benzylhydroxylamine, 1-amino-3-hydroxyaminopropane and DL-3-hydroxyamino-2-aminopropionic acid.
  • Israel Agranat, Shmuel Cohen
    1974 Volume 47 Issue 3 Pages 723-724
    Published: 1974
    Released: March 27, 2006
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    Diphenylcyclopropenone (DCP) forms 1: 1 stable crystalline complexes with dichloroacetic acid, phenylacetic acid, diphenylacetic acid, trichloroacetic acid and cyanoacetic acid. The physical properties of these complexes are consistent with a hydrogen-bonded complexation between the carbonyl oxygen of DCP and the acidic hydrogen of the substituted acetic acid.
  • Nigel James Bunce
    1974 Volume 47 Issue 3 Pages 725-728
    Published: 1974
    Released: March 27, 2006
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    Photolysis of azoxybenzene and 2,2′-azoxytoluene in the presence of 2-naphthol gives, in addition to o-hydroxyazocompounds, 1-arylazo-2-naphthols, sometimes as the major products. This implies that cleavage into diazonium ions may sometimes be a major pathway in the irradiation of aromatic azoxycompounds. A mechanism is proposed to account for the formation of azonaphthols as well as the various side products that have previously been obtained from these reactions.
  • Arabinda Ray, D. N. Sathyanarayana
    1974 Volume 47 Issue 3 Pages 729-731
    Published: 1974
    Released: March 27, 2006
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    The normal coordinate treatments of thioacetamide and its seven isotopic molecules have been carried out using Urey-Bradley force constants refined by a least-squares procedure. The laser Raman spectrum of thioacetamide has also been recorded.
  • Hajime Katô, Takahide Kimura
    1974 Volume 47 Issue 3 Pages 732-734
    Published: 1974
    Released: March 27, 2006
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    The magnetic circular dichroism (MCD) and absorption spectra of Cu(acac)2, Cu(bzac)2, Cu(TFacac)2, and Cu(TFacac)2 in benzene, chloroform, methylene chloride, 1,4-dioxane, pyridine, and piperidine are observed. The behavior of these spectra can be well explained by proposing this order of energy levels: dxz, dyz<dx2−y2<dz2<dxy. The MCD spectra in pyridine do not show any dispersion in the neighbourhood of the absorption peak which seems to correspond to the dxz, dyz→dxy transition; this fact suggests that the B-term of the MCD parameters is dominant at room temperature. There is no serious difference between the MCD of Cu(acac)2 and Cu(bzac)2, or between Cu(HFacac)2 and Cu(TFacac)2. It appears that this lowering of symmetry is not important in interpreting the MCD spectra.
  • Sadhan Basu
    1974 Volume 47 Issue 3 Pages 735-738
    Published: 1974
    Released: March 27, 2006
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    From the hole-particle description of the many-Fermion system of long chain polyenes it has been shown that the convergence limit in the electronic spectra may be accounted for by the electron-hole pairing interaction.
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