Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 47 , Issue 7
Showing 1-50 articles out of 70 articles from the selected issue
  • Kitsuma Takaishi, Isao Ando, Masahiro Kondo, Riichirô Chûj ...
    1974 Volume 47 Issue 7 Pages 1559-1563
    Published: 1974
    Released: March 27, 2006
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    The carbon-13 NMR chemical shifts of linear and branched paraffins have been calculated by means of Pople’s theory, particularly using the averaged excitation energy method. The calculation was carried out based on the CNDO/2 molecular orbital method. The values calculated by means of the averaged excitation energy method deviate extremely from the experimental ones; therefore, the energies most suitable for giving good agreement are investigated and determined for linear and branched paraffins. The suitable energies are expressed by an empirical formula, correlated to the molecular structure. The results obtained may be briefly expressed by;
    & ΔE= 11.30×1.015^a×0.958^b×1.010^c×S
    & S=1.011^d×1.009^e×1.029^f×1.009^g×1.030^h×1.031^i
    (see Results and Discussion for the notations used).
    This empirical averaged excitation energy expression is applied to cyclic hydrocarbons, such as cyclohexane, methylcyclohexane, and dimethylcyclohexane. Further, the γ-effect is estimated on the basis of these results.
  • Satohiro Yoshida, Tokuo Matsuzaki, Tomonori Kashiwazaki, Kozo Mori, Ki ...
    1974 Volume 47 Issue 7 Pages 1564-1567
    Published: 1974
    Released: March 27, 2006
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    The behavior of oxygen, O2 and O radicals adsorbed on the partially reduced V2O5–SiO2 catalysts has been investigated. Oxygen is adsorbed mainly in a molecular state at room temperature, the sum of amounts of paramagnetic adsorbed species O2 and O being less than 10% of total amount of adsorbed oxygen. High degree of reduction, high content of V2O5 and low pressure of oxygen at adsorption equilibrium are favorable for the formation of O radical. It was confirmed by the quantitative analysis of reaction products and the adsorbed species that O2, not O, is the active species in the oxidation of propylene at room temperature. A mechanism involving an intermediate of an epoxide structure was proposed.
  • Shin-ichi Shirasaki, Hiroshi Yamamura, Kunitaka Muramatsu, K\={o}ichir ...
    1974 Volume 47 Issue 7 Pages 1568-1572
    Published: 1974
    Released: March 27, 2006
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    A series of pyrochlore compounds of Pb(Tix·Sn1–x)O3, was aqueously prepared. They were characterized in terms of inhomogeneously distributed Ti and Sn ions in the equivalent lattice positions. In the composition range where the value x was between 0.00 and 0.45, monophasic pyrochlore was crystallized. In the composition range of x\gtrsim0.45, however, the pyrochlore phase more or less coexisted with a noncrystalline substance whose composition was supposed to be Pb/(Ti+Sn) mole ratio <1.0. The process of thermal transition from the pyrochlore-type Pb(Ti0.4·Sn0.6)O3 to the perovskite-type system was traced by two lines of measurements of the pyrochlore, i.e., the lattice constant and the degree of fluctuation of interplanar spacings, and by measurements of the tetragonal lattice strain of the resultant perovskite. The results showed that the transition occurred preferentially at Ti-rich microregions in the matrix lattice, in which a measurable fluctuation of the Sn: Ti ratio was detected.
  • Noboru Furusho, Tsuyoshi Komatsu, Tsurutaro Nakagawa
    1974 Volume 47 Issue 7 Pages 1573-1577
    Published: 1974
    Released: March 27, 2006
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    The thermal degradation of several halogen-containing polymers in air was studied by means of the TBA(Torsional Braid Analysis) method and IR spectroscopy. The samples were poly(vinyl chloride)(PVC), vinylidene chloride-vinyl chloride copolymer(PVdC-VC), poly(vinyl fluoride)(PVF), poly(vinylidene fluoride)(PVdF), poly(vinyl bromide)(PVB), and poly (vinylidene bromide)(PVdB). The dynamic mechanical properties of these polymers are complicated at higher temperatures because of the thermal degradation, by, for example, dehydrohalogenation. The relative shear modulus (Gr) increases and then decreases through a maximum, accompanied by changes in the logarithmic decrement. The temperatures at which the changes in Gr occur become higher in the order of PVdB<PVB<PVdC-VC<PVC<PVdF<PVF. This order agrees with that of the bond energy in carbon-halogen bonds. The apparent activation energies of these reactions were obtained from the changes in Gr and from the relative absorbance ratio of the carbon-carbon double bond with time, respectively. In general, the values estimated by these two procedures agreed well in each case.
  • Tokio Yamabe, Kazuyoshi Tanaka, Shingo Ishimaru, Kenichi Fukui
    1974 Volume 47 Issue 7 Pages 1578-1581
    Published: 1974
    Released: March 27, 2006
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    A method of calculation for the upper and lower bounds of the second-order perturbation energy is investigated. The expression for the upper bound is based on Hylleraas’s variation perturbation condition and is an improved version of that obtained by Goodisman. The lower bound is based on the Temple-type inequality and is an improved version of that by Prager and Hirschfelder. The result is numerically tested for examples of the polarizability of a hydrogen atom and the coefficients (C5 and C8) of the dispersion force between two separated hydrogen atoms, yielding fairly good results. Particularly, the results of the upper bound for C8 are the best so far calculated in a non-empirical way.
  • Tomitake Tsukihara, Yukiteru Katsube, Kumiko Fujimori, Kiyoshi Kawashi ...
    1974 Volume 47 Issue 7 Pages 1582-1585
    Published: 1974
    Released: March 27, 2006
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    As part of a program for the study of the crystal structure of copper(II)-complex with succinimide, the crystal structures of potassium tetrakis(succinimidato) copper(II) hexahydrate and lithium tetrakis(succinimidato) copper(II) monohydrate have been determined by means of X-ray analysis. In the potassium-salt, the copper atom has a square planar coordination and the potassium ion has a trigonal prismatic environment formed by six oxygen atoms. In the lithium-salt, the copper atom has a flattened tetrahedral coordination, and each lithiun ion is tetrahedrally surrounded by four oxygen atoms. The conformational difference between the complex anion of the potassium-salt and that of the lithium-salt seems to result from the different sizes of the alkali-metal ions.
  • Tetsuo Morimoto, Shigeharu Kittaka
    1974 Volume 47 Issue 7 Pages 1586-1588
    Published: 1974
    Released: March 27, 2006
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    The isoelectric point (IEP) of manganese oxide is measured on samples prepared by heating β-MnO2 and amorphous manganese oxide, MnO1.75, at temperatures from 200 to 1400°C. The IEP values thus obtained are characteristic of each stage of the oxidation of manganese oxide; that is, <5.1 for MnO2, 7.6–9.0 for α-Mn2O3, and 3.3–5.2 for Mn3O4. These values can be explained by the electrostatic interaction theory introduced by Parks, in which the CFSE correction is eliminated. It is also found that manganese ions with specific valencies are responsible for the electrification of the surfaces of manganese oxide.
  • Yoshio Matsunaga, Ryuzo Osawa
    1974 Volume 47 Issue 7 Pages 1589-1592
    Published: 1974
    Released: March 27, 2006
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    When 2,4,6-trinitrobenzoic acid is combined with aromatic monoamines, true benzoates are mostly formed. However, not only a white true benzoate, but also a red 2 : 1 complex of the CPT type, in which charge-transfer and proton-transfer interactions operate simultaneously between the component molecules, were obtained with aniline. In addition, the brown 2,4,5-trimethylaniline complex reported by Noelting and Sommerhoff was found to be of a similar nature. The phenomenon of complex isomerism was observed upon combination with o-chloroaniline; that is, the colorless salt isomerizes into an orange-colored charge-transfer complex at about 133 °C. Only the complexes with p-dimethylaminobenzaldehyde and o-nitroaniline, which have the lowest pKa values among the amines examined, and those with the halogenated 2-naphthylamines are of the charge-transfer type. The 3,5-dinitrobenzoic acid complexes were also examined. Complexes of the CPT type with a 3: 2 composition were isolated with aniline and p-toluidine.
  • Masahiko Nakamura, Hiroaki Takahashi, Keniti Higasi
    1974 Volume 47 Issue 7 Pages 1593-1595
    Published: 1974
    Released: March 27, 2006
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    The dielectric constants and losses of dilute solutions of anthrone, xanthone, phenothiazine, 9-fluorenone, benzophenone, diphenylnitrosamine, 1,8-dinitronaphthalene, p-nitrotoluene and m-nitrophenol in o-terphenyl have been measured in the supercooled state in the frequency range 1–100 MHz and temperature range 15–30 °C. The results have been analyzed by Davidson-Cole’s skewed-arc method to calculate the relaxation times, the distribution parameters, the activation enthalpies and entropies for the dielectric relaxation processes.
  • Kimiko Mizutani, Kimiko Miyazaki, Kimiko Ishigaki, Haruo Hosoya
    1974 Volume 47 Issue 7 Pages 1596-1603
    Published: 1974
    Released: March 27, 2006
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    Ultraviolet absorption, fluorescence, and excitation spectra of xanthone and its hydroxyl and methoxyl derivatives were measured in sulfuric acid solutions of various acidities. The basicities (pKa’s) of these compounds were obtained from the spectral change. Variable-β type molecular orbital calculations of the π-systems were performed, assignment of the absorption spectra being made. It was confirmed that protonation occurs at the carbonyl oxygen atom. A method for obtaining the equilibrium constant without knowing the absolute intensity is proposed.
  • Akira Kuboyama, Sanae Matsuzaki, Hiroshi Takagi, Hiroshi Arano
    1974 Volume 47 Issue 7 Pages 1604-1607
    Published: 1974
    Released: March 27, 2006
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    The π–π* absorption spectra of p-benzoquinone, α-naphthoquinone, anthraquinone, and their derivatives, mainly in n-heptane up to the vacuum UV region, were obtained. On the other hand, MO calculations of the n-electronic systems of these p-quinones and o-benzoquinone were carried out by means of the P-P-P method. The π–π* absorption bands of these quinones could be favorably assigned on the basis of the calculated results.
  • Kazuhiko Seki, Yoshiya Harada, Koichi Ohno, Hiroo Inokuchi
    1974 Volume 47 Issue 7 Pages 1608-1610
    Published: 1974
    Released: March 27, 2006
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    The photoelectron spectrum of naphthacene polycrystal was obtained with a high-resolution photoelectron spectrometer using a helium 21.22 eV light source, and the vibrational fine structures were examined. The resolution, 21 meV FWHM for the argon P3⁄2 peak, became much better than that obtained by means of a retardingpotential-type electron analyzer. Broad peaks with no distinct intramolecular vibrational structure were observed, and the origin of the peak width was discussed.
  • Masaaki Ogasawara, Seizo Inaba, Hiroshi Yoshida, Koichiro Hayashi
    1974 Volume 47 Issue 7 Pages 1611-1615
    Published: 1974
    Released: March 27, 2006
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    Evidence was obtained by ESR for the ion-pair formation between the tetracyanoethylene anion radical and the cesium counterion in tetrahydrofuran. The hyperfine lines of the ESR spectrum of cesium tetracyanoethylenide were exceptionally broad at high salt concentrations in tetrahydrofuran, while they were remarkably narrowed by the addition of a small amount of DMF or triglyme (cation-solvating agents) or by replacing the counterion with the tetra-n-butylammonium ion. This indicates that the broad linewidth is due to the unresolved hyperfine splitting of the cesium counterion. In addition, the concentration dependence of the ESR spectrum indicates that the line broadening is to be interpreted not only in terms of the Heisenberg spin exchange, but also in terms of the equilibrium between the ion-pair and the free ion. The cesium hyperfine coupling constant was estimated by simulating the line shape to be 40 m Gauss in the ion-pair state between the tetracyanoethylene anion radical and the cesium ion in the tetrahydrofuran solution.
  • Shuzo Shibata, Fumihiko Hirota, Yukio Ota
    1974 Volume 47 Issue 7 Pages 1616-1618
    Published: 1974
    Released: March 27, 2006
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    The hydrogen bonded system of H2O–HCl was studied by the CNDO/2 method. Calculation of the potential energy for the system showed that the complex of H2O–HCl is considerably stable. The equilibrium structure of the complex and its charge distribution were also investigated.
  • Tsutomu Minato, Shinichi Yamabe, Satoshi Inagaki, Hiroshi Fujimoto, Ke ...
    1974 Volume 47 Issue 7 Pages 1619-1623
    Published: 1974
    Released: March 27, 2006
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    A semiempirical SCF MO calculation of the reaction between ethylene and diazomethane was carried out as an example of 1,3-dipolar cycloaddition. A calculation of the interaction energy and electron population by the use of the configuration interaction wave function showed that the formation of the two new bonds in this reaction is concerted but non-synchronous. This result is attributable to the extension of the highest occupied molecular orbital of diazomethane.
  • Tatsuo Horiba, Ken-ichi Hara, Motomichi Inoue, Masaji Kubo
    1974 Volume 47 Issue 7 Pages 1624-1626
    Published: 1974
    Released: March 27, 2006
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    The magnetic susceptibility of magnesium 2,2′-dipyridylide has been determined in its THF (tetrahydrofuran) adducts in a temperature range of 1.6–20 K. The susceptibility of Mg(dipy)2.THF exhibits two maxima at about 3.9 and 9.5 K due to short range and long-range interactions, respectively. The observed susceptibility conforms to the alternating linear Heisenberg model above about 6 K. Mg(dipy)2·3THF shows no definite maximum of magnetic susceptibility. The magnetic behavior of these complexes different from that of Be(dipy)2 is attributable to the difference in the ionic character between Mg–N and Be–N bonds.
  • Shozo Shimizu, Shinji Kekka, Setsuo Kashino, Masao Haisa
    1974 Volume 47 Issue 7 Pages 1627-1631
    Published: 1974
    Released: March 27, 2006
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    Crotonic acid crystallizes in the monoclinic space group C2/c, with a=15.30(3), b=4.06(1), c=16.18(2) Å, β=107.4(1)° and Z=8; crotonamide in the monoclinic space group P21/a, with a=9.71(2), b=6.90(2), c=7.75(1) Å, β=104.0(4)° and Z=4. The structures have been solved by the Patterson method and refined by the block-diagonal least-squares method. The final R values are 0.090 for 337 observed reflections for crotonic acid, and 0.088 for 525 observed ones for crotonamide. The configuration of the molecules of crotonic acid and crotonamide is approximately planar and of trans-type regarding the C=C bond. Every two centrosymmetrically related molecules form a dimer through hydrogen bonds of 2.645 Å (OH···O) for crotonic acid and 2.963 Å (NH···O) for crotonamide. In the crystals of crotonamide additional NH···O hydrogen bonds (2.862 Å) link the neighboring molecules related by the a-glide plane to form a sheet parallel to (001) plane. Distances between the C=C bonds of the nearest neighbors are 3.86 Å for crotonic acid and 3.62 and 3.88 Å for crotonamide.
  • Katsuhiko Takaya, Norio Ise
    1974 Volume 47 Issue 7 Pages 1632-1635
    Published: 1974
    Released: March 27, 2006
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    The temperature dependence of UV spectra of fluorenyl lithium and sodium was investigated in 30, 40, and 50 vol% dimethoxyethane (DME)–benzene mixtures. The lithium salt had two absorption peaks at 352 and 373 nm, and the sodium salt at 358 and 373 nm. The fraction of solvent-separated ion pairs for the sodium salt was much lower than that of the lithium salt, and the heat of conversion (−ΔHi) of contact-ion pairs to solventseparated ion pairs was larger (9–11 kcal/mol) for the sodium salt than that (1–4 kcal/mol) for the lithium salt.
  • Masahiro Komatsu
    1974 Volume 47 Issue 7 Pages 1636-1641
    Published: 1974
    Released: March 27, 2006
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    The polarography of several aliphatic polyamine complexes of Pb(II), Zn(II), and Ni(II), and the anodic stripping polarography of polyamine complexes of Zn(II), Cd(II), Pb(II), and Cu(II) were studied. The aliphatic polyamines used were ethylenediamine(en), 1,3-propanediamine(1,3-pn), 1,2-propanediamine(1,2-pn), diethylenetriamine(den), and triethylenetetramine(trien). These lead(II) complexes gave a one-step reversible wave which was diffusion-controlled. The relation between the logarithm of the concentration of polyamine and the halfwave potential of the Pb(II) complex was straight, so that one species of complex ion was found to be predominant in the bulk of solution. The ionic species in the bulk of solution were found to be Pb(en)22+, Pb(1,3-pn)22+, Pb(1,2-pn)22+, Pb(den)22+, and Pb(trien)2+. The stability constants of these complexes were calculated and were found to increase in the order of Pb(1,3-pn)22+<Pb(en)22+<Pb(1,2-pn)22+<Pb(den)22+<Pb(trien)2+. The polarographic waves of Zn(II)-polyamine and Ni(II)-polyamine complexes were irreversible and diffusion-controlled, so the electrode reactions of these complexes were assumed using Matsuda-Ayabe’s theory. All these polyamine complexes of Zn(II), Cd(II), Pb(II), and Cu(II) gave well-defined anodic stripping polarograms. 1,3-pn was the best complexing reagent among these polyamines, because it gave the best separation of the peaks of the anodic stripping polarograms of the four metal ions. Calibration curves were obtained from 0.01 to 0.10 ppm for Zn(II), Pb(II), and Cu(II), and from 0.001 to 0.010 ppm for Cd(II) in 0.4 M 1,3-pn and 0.2 M KCl media. The effects of acid and base on the anodic stripping polarograms were also studied.
  • Yoshio Shijo
    1974 Volume 47 Issue 7 Pages 1642-1645
    Published: 1974
    Released: March 27, 2006
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    The solvent extraction of the copper–Pyrocatechol Violet chelate with tridodecylethylammonium bromide (abbreviated TDEA) in benzene as an ion-association system has been investigated by the spectrophotometric method. The copper–PV–TDEA complex can be extracted into such aromatic hydrocarbons as benzene, toluene, and xylene, but not into such polar solvents as n-butanol, ethyl acetate, methylisobutylketone, and nitrobenzene. When a sample solution containing copper and PV, the pH of which has been adjusted to 7.5–8.5, is shaken with TDEA in benzene for 10 s, the maximum extraction of the ternary complex is obtained. The extractability of the complex from 50 ml of an aqueous solution into 10 ml of benzene is 98.3% under the optimum conditions. The absorbance and stability of the complex increase upon the addition of a small amount of ethanol to the extracted layer. Beer’s law is obeyed up to 6.5 μg copper per 10 ml of benzene, and the molar absorptivity of the complex is 7.9×104 cm−1·mol−1·l at 663 nm. The composition of the complex is confirmed to be Cu:PV: TDEA=1: 2: 2 by the continuous variation method. A structure for the complex is proposed.
  • Masao Kiyama
    1974 Volume 47 Issue 7 Pages 1646-1650
    Published: 1974
    Released: March 27, 2006
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    The optimum conditions were studied for the formation of Fe3O4 by the air oxidation of Fe(OH)2. The suspensions obtained by mixing NaOH and FeSO4 solutions in various values of R(=2NaOH/FeSO4) were subjected to oxidation with air at various temperatures. The oxidation products were then examined by X-ray powder diffraction, chemical analysis, electron microscopic observation, and BET surface-area determination. Fe3O4 is formed at higher temperatures than is FeOOH. The temperature of formation becomes low as R approaches 1.0. In neutral suspensions (R<1), Fe3O4 is formed via green rust II or a mixture of green rust II and Fe(OH)2. By further oxidation, the Fe3O4 formed gradually changes to γ-Fe2O3. A mixture of α-FeOOH and either NaFe3(OH)6(SO4)2 or α-Fe2O3 is formed as the final oxidation product. In alkaline suspensions (R>1), Fe3O4 is formed directly. The morphology and ferrous-ion content of Fe3O4 powder change considerably with the presence of green rust II before the formation of Fe3O4. It is suggested that Fe3O4 is formed near the surface of the particles of Fe(OH)2 and green rust II by the coprecipitation of ferrous ions with ferric hydroxo-complexes.
  • Kunio Shimizu, Tadashi Matsubara, Gen P. Satô
    1974 Volume 47 Issue 7 Pages 1651-1656
    Published: 1974
    Released: March 27, 2006
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    The reduction of [Ru(Hedta)(H2O)] at the mercury electrode and the subsequent chemical reactions in buffer solutions were investigated by AC and DC polarography and by large-scale electrolysis. Two polarographic steps were observed; the more positive step is discussed in this paper. The step was a diffusion-controlled, one-electron reduction of ruthenium(III) to ruthenium(II). For [H+]=(10−3–10−5) mol dm−3 the reduction was reversible, and it became less reversible if [H+]<10−5 mol dm−3. Large-scale electrolysis in formate buffer solutions at the potential of the polarographic diffusion current plateau confirmed that the reduction is a one-electron process. In formate buffer, the reduced form of the complex is deactivated. Furthermore, in the presence of perchlorate ions the reduced form is reoxidized to the original form. The rate constant for the reoxidation reaction at 25.0 °C was k2=(1.38±0.26)×10−3 mol−1 dm3 s−1. The activation parameters for the reoxidation reaction were ΔH\ eweq=(94.1±17.6)×103J mol−1 and ΔS\ eweq=(19.0±6.3) J K−1 mol−1.
  • Kosuke Izutsu, Toshiaki Nomura, Toshio Nakamura, Hidetoshi Kazama, Shi ...
    1974 Volume 47 Issue 7 Pages 1657-1660
    Published: 1974
    Released: March 27, 2006
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    The complexing of the sodium ion in acetonitrile (AN) with such solvents as methanol, water, DMF, DMA, DMSO, HMPA, and pyridine has been studied potentiometrically by using a monovalent cation-sensitive glass electrode. The reference electrode of Ag-0.005 M AgNO3(AN) and the salt bridge of 0.1 M Et4NPi(AN) were used. Mono- and di-solvated ions were formed for methanol, water, and pyridine. For DMF, DMA, DMSO, and HMPA, tri-solvated species were also formed. The formation constants for the mono-solvated sodium ion were 0.7 for pyridine, 1 for methanol, 1.8 for water, 2.5 for DMF, 5 for DMA, 6 for DMSO, and 30 for HMPA.
  • Hayami Yoneda, Katsuhiko Miyoshi, Shingo Suzuki, Toshiaki Taura
    1974 Volume 47 Issue 7 Pages 1661-1664
    Published: 1974
    Released: March 27, 2006
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    The effect of ethanol on the outer-sphere association of Λ- or Δ-[Coen3]3+ ion (en=ethylenediamine) with d-tartrate ion was investigated in aqueous solutions containing 0,1,3, and 5 wt% of ethanol at 25 °C by measuring the change in optical density of the charge-transfer spectra at 265 nm. It was found that the association constant of Λ-[Coen3]3+ ion with d-tartrate ion KA(Λ) was a little larger than that of Δ-[Coen3]3+ ion KA(Δ), and that the addition of ethanol increased both KA(Λ) and KA(Δ) but decreased the ratio KA(Λ)KA(Δ). The diminished discrimination between Λ- and Δ-[Coen3]3+ ions by d-tartrate ion was discussed in terms of the solubility of these diastereoisomers in aqueous ethanol and was attributed to the increased electrostatic interaction between the complex and d-tartrate ions arising from the decrease in the dielectric constant of the medium.
  • Hidetake Kakihana, Shin-ichi Ishiguro
    1974 Volume 47 Issue 7 Pages 1665-1668
    Published: 1974
    Released: March 27, 2006
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    The stability constants and the molar extinction coefficients of uranium(IV) fluoride complexes were determined in aqueous solutions containing 1 M (Na++H+)Cl as a constant ionic medium at 25 °C. The emf data obtained by the use of a fluoride-ion-selective electrode were explained in terms of the formation of a series of mononuclear complexes, UF3+, UF22+, UF3+, and UF4, with stability constants β1=(2.2±0.13)×107, β2=(1.33±0.05)×1013, β3=(2.9±0.5)×1017, and β4=(6±1)×1021 respectively. Using these values for β’s the spectra observed in the 350–700 nm region were analyzed by means of a computer in order to estimate the molar extinction coefficients of each uranium(IV) fluoride complex species.
  • Mitsunori Tanaka, Hisashi Okawa, Tomoko Tamura, Sigeo Kida
    1974 Volume 47 Issue 7 Pages 1669-1672
    Published: 1974
    Released: March 27, 2006
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    Copper(II) and nickel(II) complexes of H2fsac-R have been synthesized, where H2fsac-R denotes the Schiff bases prepared from 3-formylsalicylic acid and alkylamines (alkyl(R)=methyl, ethyl, hydroxyethyl, n-propyl, n-butyl, isobutyl, and sec-butyl). On the bases of elemental analyses, IR spectra, visible spectra and cryomagnetic measurements, it was found that the complexes have a binuclear structure connected by two phenolic oxygens; the complexes are abbreviated to M2(fsac-R)2. The nickel(II) complexes contain two, three or four molecules of coordinated water. The cryomagnetic data for Cu2(fsac-R)2 are interpreted in terms of the Bleaney-Bowers equation with large −2 J values (>700 cm−1), indicating the presence of strong intramolecular antiferromagnetic spin-exchange interactions. The Ni2(fsac-R)2·nH2O obey the Curie-Weiss law, the Weiss constants being estimated to −35–−41 K.
  • Sadao Tsuboi, Yasuhiro Ishiguro, Akira Takeda
    1974 Volume 47 Issue 7 Pages 1673-1677
    Published: 1974
    Released: March 27, 2006
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    The Diels-AIder reaction of 5,5,5-trichloro-3-penten-2-one (1a) with cyclopentadiene afforded exo-2-acetyl-endo-3-trichloromethylbicyclo[2.2.1]hept-5-ene (2a) stereoselectively. The stereochemistry of the reactions of cyclopentadiene with several γ-chlorinated α,β-unsaturated ketones was examined. The endo-directive abilities decreased in the following order: CCl3>CCl2CH3, CHCl2, CCl(CH3)2>CH(CH3)2>CH3. Compound 1a reacted with butadiene and furan to give 4-acetyl-5-trichloromethylcyclohexene (3) and 4-(2-furyl)-5,5,5-tri-chloropentan-2-one (7) respectively.
  • Tetsuko Miyauchi, Yutaka Kadokura, Naoaki Fukada, Tatsuo Takeshima
    1974 Volume 47 Issue 7 Pages 1678-1679
    Published: 1974
    Released: March 27, 2006
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    1,3-Thiazines, (1)–(6), were synthesized, in yields ranging from 2.9 to 43%, by the reaction of aldehyde with the intermediate β-iminodithiocarboxylic acids which are formed by the reaction of ketones with carbon disulfide in the presence of ammonia.
  • Nobuo Ishikawa, Akira Sekiya
    1974 Volume 47 Issue 7 Pages 1680-1682
    Published: 1974
    Released: March 27, 2006
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    Molecular iodine in the system of thallium(III) trifluoroacetate-trifluoroacetic acid has been found to possess a high potency for aromatic iodination. Under controlled conditions, benzene and also mesitylene were stepby-step mono-, di-, and triiodinated, whereupon whole iodine was consumed for the iodination by the oxidation process of the thallium(III) salt. In the course of the iodination of benzene, an intermediate has been revealed to consist of thalliated benzenes, which were transformed into iodinated benzenes by the electrophilic attack of iodine.
  • Hiroshi Horino, Mannosuke Arai, Naoto Inoue
    1974 Volume 47 Issue 7 Pages 1683-1686
    Published: 1974
    Released: March 27, 2006
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    The reaction of 1,2-dihydronaphthalene, indene, and acenaphthylene with phenylpalladium chloride prepared in situ from phenylmercuric chloride and lithium chloropalladate in aqueous acetone afforded 2-phenyltetrarol, 2-phenylindanol, and 2-phenylacenaphthenol respectively, accompanying by the corresponding phenylated olefins. Acetoxyphenylation products were also obtained in the reactions in acetic acid. The configurations of these oxyphenylated compounds were determined to be trans.
  • Masaaki Iwata, Sakae Emoto
    1974 Volume 47 Issue 7 Pages 1687-1692
    Published: 1974
    Released: March 27, 2006
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    9-Substituted 2-methoxyanthracenes (IVa–d) and -triptycenes (Va, b), and 3-substituted anisoles (VIa, b) were formylated by the use of the Vilsmeier-Haack method (Method A) and the metallation method using n-butyllithium (Method B). By the Method A, IVa–c, Vs’, and VIs’ were regioselectively formylated at C-1, C-3, and C-6 respectively, without exception, while by the Method B IVa–c, Va, VIa, and VIb were regioselectively formylated at C-3, C-3, C-2, and C-6 respectively, and Vb gave C-1 and C-3 formylated derivatives in the ratio of 10 to 1 respectively. Possible transition states concerning the occurrence of the regioselectivity were proposed and discussed.
  • Seiji Arimatsu, Ryohei Yamaguchi, Mituyosi Kawanisi
    1974 Volume 47 Issue 7 Pages 1693-1697
    Published: 1974
    Released: March 27, 2006
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    The thermal treatment of 4-homoadamantanol and bicyclo[3.3.1]nonanols with hexamethylphosphoric triamide (HMPT) gave the corresponding olefins in moderate yields. The application of this dehydration method to a system in which olefin formation was regarded as difficult or impossible stereochemically led to various types of reactions, i.e., reduction, substitution, and phosphorodiamidation. Upon being heated in HMPT, 2-adamantanol afforded 2-adamantyl tetramethylphosphorodiamidate, whereas 1-adamantanol was transformed into adamantane via 1-adamantyl tetramethylphosphorodiamidate. In the case of allylic or benzylic alcohols, dimethylamino-substituted compounds were obtained. The reduction of the amount of HMPT promoted the formation of an ether, while dibenzhydryl ether was produced exclusively from benzhydrol. The mechanism of these reaction is discussed.
  • Masato Tanaka, Yoshihisa Watanabe, Take-aki Mitsudo, Yoshinobu Takegam ...
    1974 Volume 47 Issue 7 Pages 1698-1703
    Published: 1974
    Released: March 27, 2006
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    The effects of the reaction conditions on the asymmetric hydroformylation of styrene with rhodium catalysts have been studied. The [α]D value and the configuration of the product, hydratropaaldehyde, were much affected by the phosphine/rhodium ratios, the reaction temperatures (20–110 °C), and the partial pressures of carbon monoxide and hydrogen (10–100 atm). The results were mainly explained in terms of the structures of the catalysts and the skeletal isomerization of acyl complexes. The predominant species of the catalysts and the participation of π-benzyl-type intermediate were also discussed.
  • Chikahiko Eguchi, Akio Kakuta
    1974 Volume 47 Issue 7 Pages 1704-1708
    Published: 1974
    Released: March 27, 2006
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    L-Hydroxyproline (1) and D-allo-hydroxyproline (2) were synthesized from D-glutamic acid (3) using the asymmetric center of 3 as that at C4 of 4-hydroxyproline. When the aqueous solution of 1 or 2 was heated at 200 °C for 2 hr, a solution in the equilibrium state, containing 55% of 1 and 45% of 2, was obtained. From this mixture, 1 was obtained by fractional crystallization.
  • Kunio Okamoto, Koichi Komatsu
    1974 Volume 47 Issue 7 Pages 1709-1711
    Published: 1974
    Released: March 27, 2006
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    The zinc reduction of the tropylium ion was carried out in the presence of 2-methyl-2-nitrosopropane (a radical scavenger) in H2O–THF (7:3 by volume) at room temperature. In the reaction mixture with a short reaction time (5 min), t-butyl tropyl nitroxide (II) (a radical-trapping product) was identified by the ESR analysis. α-Phenyl-N-t-butylnitrone (I), which was isolated from the reaction mixture during a prolonged reaction time (30 min), was proved to be derived from the nitroxide II through the hydrogen abstraction by t-butyl nitroxide, which was itself formed from 2-methyl-2-nitrosopropane in situ in the acidic reaction mixture in the presence of zinc powder. The hydrogenation (on Pd/C) of the product mixture for a short reaction time (1 min) gave N-t-butyl-N-cycloheptylhydroxylamine and bicycloheptyl. On the basis of these observations, it is concluded that the primary product of the zinc reduction of the tropylium ion must be the tropyl radical.
  • Hiroo Inoue, Megumu Izumi, Eiji Imoto
    1974 Volume 47 Issue 7 Pages 1712-1716
    Published: 1974
    Released: March 27, 2006
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    The thermal and photochemical reactions of toluene with anhydrous iron(III) chloride in the solid state result in nuclear chlorination. In a homogeneous system, a side-chain reaction occurs under irradiation with light, although no product is obtained in the thermal reaction. The addition of water to the iron(III) chloride–toluene system in the range of the molar ratio of 1–5 changes the course of the photochemical reaction; in the water/iron(III) chloride molar ratios of 1–1.7, 3, and 4–5, the main products are the diphenylmethane-type compound, o- or p-chlorotoluene (o>p), and benzyl chloride respectively. Pyridine as a ligand acts to give benzyl chloride selectively. The Mössbauer data of the FeCl3/nH2O solid show that the arrangement of the Cl ion around the Fe(III) ion changes upon the addition of water. The thermal and photochemical reactions of p-methoxytoluene with anhydrous iron(III) chloride give 2,2′-dimethoxy-4,4′-dimethylbiphenyl by oxidative aryl coupling. Water inhibits the aryl coupling reaction.
  • Yoshie Souma, Hiroshi Sano
    1974 Volume 47 Issue 7 Pages 1717-1719
    Published: 1974
    Released: March 27, 2006
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    In the presence of an Ag carbonyl-ion catalyst, prepared in situ from the Ag compound and carbon monoxide in H2SO4, olefins or alcohols reacted with carbon monoxide at room temperature and atmospheric pressure to produce exclusively tertiary carboxylic acids in high yields. The amount of Ag compound sufficient for carrying out the reaction is ca. 0.2 mol/l. The optimum reaction temperature is 0–40°C. The reaction proceeds practically at above a 90% H2SO4 concentration. Saturated hydrocarbons, containing a tertiary hydrogen, also reacted with carbon monoxide in the presence of alcohols or olefins as carbonium ion precursors, thus producing tertiary carboxylic acids.
  • Hiroaki Uchida, Akiko Chinone, Masaki Ohta
    1974 Volume 47 Issue 7 Pages 1720-1723
    Published: 1974
    Released: March 27, 2006
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    The reaction of 2-benzoylamino-2-methylpropionamidine (III) with 1,3-bifunctional compounds was investigated in connection with studies on 2-benzoylaminoacetamidine(I). In case of the reaction of III an appreciable amount of 5,5-dimethyl-2-phenylimidazolin-4-imide (VIII) was formed, the yield of 2-(1-benzoylamino-1-methylethyl)-4,6-dimethylpyrimidine (VI) being low. On the other hand, III reacted with ethyl acetoacetate to give 2-(1-benzoylamino-1-methylethyl)-4-hydroxy-6-methylpyrimidine (IX) in about 50% yield besides VIII. Both III and I were made to react with ethoxymethyleneacetylacetone to yield 5-acetyl-2-(1-benzoylamino-1-methylethyl)-4-methylpyrimidine (X) and 5-acetyl-2-(N-benzoylaminomethyl)-4-methylpyrimidine (XI), respectively. Reaction of I with ethoxymethylenemalononitrile gave 4-amino-2-(N-benzoylaminomethyl)-5-cyanopyrimidine (XII), but did not proceed with benzoin, malondialdehyde, tetraethoxypropane or phenacyl bromide.
  • Teruo Matsuura, Yoshikatsu Ito
    1974 Volume 47 Issue 7 Pages 1724-1726
    Published: 1974
    Released: March 27, 2006
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    Photoaromatization of various dihydroheteroaromatics and some carbocyclic dihydroaromatics with excited acetone was examined. Among the tested compounds, indoline, 2,3-dihydro-2-methylbenzofuran, and 9,10-dihydroanthracene were found to be photoaromatized. 2-Thiazolines, 2-oxazolines, 2-isoxazolines, 9,10-dihydrophenanthrene, 2,3-dihydro-5,6-dimethylpyrazine, 3,4-dihydro-1-methylisoquinoline, and 6-methyl-3(2H)-pyridazinone did not undergo photoaromatization, but recovered unchanged or underwent their own photochemical reactions.
  • Eric Brown, Michel Ragault
    1974 Volume 47 Issue 7 Pages 1727-1728
    Published: 1974
    Released: March 27, 2006
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    The rule of maximum compactness is put forward as a guide for establishing the stereochemistry of catalytic hydrogenation in many cases. This rule complements the well-known Auwers-Skita rule.
  • Eric Brown, Michel Ragault
    1974 Volume 47 Issue 7 Pages 1729-1730
    Published: 1974
    Released: March 27, 2006
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    The stereochemistry is given of various perhydrobenz(e) inden-2-ones, which have been synthesized as potential intermediates for C-nor-D-homo-steroids.
  • Tetsuo Suami, Seiichiro Ogawa, Shuichi Oki, Haruo Sato
    1974 Volume 47 Issue 7 Pages 1731-1736
    Published: 1974
    Released: March 27, 2006
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    Reactions of azide ion with three disulfonates (1,4-, 1,5-, and 1,6-) of myo-inositol and its 1,2-O-cyclohexylidene derivative were studied. The structures of the new azido compounds thus obtained were established by PMR spectroscopy and reaction sequences. The reaction mechanisms of the neighboring-group participation reactions were discussed. Hydrogenation of the azido compounds followed by acetylation afforded the corresponding six inosadiamines as their hexaacetates: three known (allo-1,5, muco-1,3, and myo-4,5) and three hitherto unknown inosadiamines (allo-1,4, muco-1,2, and chiro-2,4).
  • Tetsuo Suami, Seiichiro Ogawa, Shuichi Oki, Hideo Kunitomo
    1974 Volume 47 Issue 7 Pages 1737-1743
    Published: 1974
    Released: March 27, 2006
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    Reactions of the azide ion with four trisulfonates (1,4,5-, 1,4,6-, 1,5,6-, and 4,5,6-) and one tetrasulfonate (1,4,5,6-) of myo-inositol were studied. The structures of the new azido compounds were established by PMR spectroscopy and reaction sequences. The mechanism of neighboring-group participation reactions were discussed.
  • Isao Kamiya, Keizo Aoki
    1974 Volume 47 Issue 7 Pages 1744-1749
    Published: 1974
    Released: March 27, 2006
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    In the course of our studies of the chemiluminescence of xanthene dyes, we found the violet chemiluminescence emission (CL-emission) resulting from the reaction of succinylfluorescein with oxygen in an aerated alkaline aqueous system of a high concentration of an aprotic solvent (DMSO or DMF), an especially intense emission occurring in aerated dry DMSO or DMF with tert-BuOK as base. The CL-emission comprised two emission components: an intense violet emission (a peak, at 410 nm) whose spectral distribution was similar to that of the fluorescence band which appeared during the course of the reaction, and a weak greenish-yellow emission similar to the fluorescence of the dye. By isolating and identifying the violet-fluorescent reaction product with an authentic sample, and by comparing the CL-emission with the fluorescence emission of the isolated product, it was concluded that the violet CL-emission may be attributed to the formation of an excited dianion of 3,6-dihydroxyxanthone. The reaction path leading to the dioxetane intermediate which will be produced by the elimination of a proton from the C atom at the β-position of the dye, followed by the oxygenation via the caged radical pair, was discussed as a likely mechanism for the formation of the excited dianion.
  • Tetsuo Nozoe, Kahei Takase, Tomoo Nakazawa, Satoko Sugita, Motoyasu Sa ...
    1974 Volume 47 Issue 7 Pages 1750-1753
    Published: 1974
    Released: March 27, 2006
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    The reaction of 3-(ω-ethoxycarbonylacetyl)-2H-cyclohepta[b]furan-2-one (4) with malononitrile and with cyanoacetamide, in the presence of sodium ethoxide, gave 4-hydroxyazuleno[2,1-b]pyrid-2(1H)-one derivatives, (5) and (9) respectively, in good yields. On the other hand, the reaction of 4 with ethyl cyanoacetate gave 3-cyano2-ethoxycarbonylmethylazulene-1-carboxylic acid (12). The structures of these products were determined on the basis of the spectral data and some chemical evidences.
  • Akira Sera, Hiroshi Mano, Kazuhiro Maruyama
    1974 Volume 47 Issue 7 Pages 1754-1757
    Published: 1974
    Released: March 27, 2006
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    Esters of phenylsulfonylacetic acid were found to undergo a base-induced β-elimination reaction with t-butoxide in t-butyl alcohol. The intervention of a carbanion as an intermediate of the elimination was proposed. The stereochemistry of the elimination was examined by the use of erythro and threo-2-deuterio-1,2-diphenylethyl phenylsulfonylacetates. From the deuterium content in a product, i.e., trans-stilhene, the elimination was found to occur predominantly in a syn fashion.
  • Hiroshi Mano, Akira Sera, Kazuhiro Maruyama
    1974 Volume 47 Issue 7 Pages 1758-1760
    Published: 1974
    Released: March 27, 2006
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    The base-induced elimination reaction of 1,2-diphenylethyl phenylsulfonylacetate was investigated in a variety of base–solvent systems. A stronger base was found to facilitate syn elimination. The addition of crown ether caused a remarkable change in the stereochemistry of elimination from syn to anti. In aprotic solvents, an overwhelming syn elimination was observed.
  • Michiaki Hashimoto, Yasumi Shimizu, Fumio Ogura, Masazumi Nakagawa
    1974 Volume 47 Issue 7 Pages 1761-1766
    Published: 1974
    Released: March 27, 2006
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    Isomeric 3- or 4-chlorotriptycene-7-carboxylic acid was synthesized from sodium anthraquinone-β-sulfonate and resolved with quinidine methohydroxide. The absolute configurations of (−)-3-chloro- and (−)-4-chlorotriptycene-7-carboxylic acids could be determined to be 1S,6S and 1S,6R, respectively, by the chemical correlation with (+)-2,5-dimethoxy-8-chlorotriptycene whose absolute configuration was proved to be 1R,6S by X-ray and chemical means.
  • Hitoshi Takeshita, Akira Mori, Shô Itô
    1974 Volume 47 Issue 7 Pages 1767-1769
    Published: 1974
    Released: March 27, 2006
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    The irradiation of methyl acetopyruvate with cycloheptatriene by means of a high-pressure mercury lamp has yielded (6+2)π and (4+2)π cycloadducts, together with tropylcarbinol derivatives formed by a formal abstraction of allylic hydrogen by the excited carbonyl group, this being the major process in this reaction.
  • Kunio Okamoto, Tomomi Kinoshita, Osamu Makino
    1974 Volume 47 Issue 7 Pages 1770-1776
    Published: 1974
    Released: March 27, 2006
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    Phenolyses of optically active 1-phenylethyl chloride were carried out in phenol (50°C), p-cresol (100°C), p-chlorophenol (100°C), and 2,6-xylenol (100°C in the presence of variable concentrations of the sodium salts of the respective phenols or triethylamine; the distributions (%) for the O- and C-alkylation products and the net steric courses (α%) for each product were examined. The distribution and the steric course which were graphically extrapolated to the zero base concentration indicated that, if the influence of the liberated hydrogen chloride was excluded, in the phenolyses without an added base the major products are the 1-phenylethyl ethers of the respective phenols with net retained configurations and the minor products are the o-and p-1-phenylethylated phenols with net inverted configurations. The hydrogen chloride rearrangement of the optically active 1-phenylethyl ethers of the respective phenols proceeded rapidly to give o-1-phenylethylated phenols with predominantly retained configurations (for phenol, p-cresol, and p-chlorophenol) and p-1-phenylethylated phenols with net inverted configurations (for phenol and 2,6-xylenol) in the respective phenol–benzene (1:1 by wt) solvents. The p-toluenesulfonic acid rearrangement of 1-phenylethyl phenyl ether-18O proceeded to give o- and p-1-phenylethylphenols with partial loss of the oxygen-18 atom in the phenol–benzene (1:1 by wt) solvent, indicating the coexistence of the intermolecular course for the acidic rearrangement in the phenolic solvents. From these findings, it is concluded that the formation of the ortho-alkylates with retention of configuration, experimentally observed in the respective phenolyses without an added base, is attributed not to the direct retentive alkylation of the phenols, but to the rapid rearrangement of the 1-phenylethyl ethers with net retention of configuration, caused by the hydrogen chloride liberated in the SN1-phenolysis of 1-phenylethyl chloride in the respective phenolic solvents.
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