Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 42 , Issue 10
Showing 1-50 articles out of 85 articles from the selected issue
  • Reiichi Yamane, Toshikatsu Sata, Yukio Mizutani, Yasuharu Onoue
    1969 Volume 42 Issue 10 Pages 2741-2748
    Published: 1969
    Released: March 27, 2006
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    The effect of the condition of the diffusion-boundary layer in the ion-exchange membrane electrodialysis on the limiting-current density and on the relative transport numbers of ionic species with the same sign was studied. The limiting-current density in the laminar flow is approximately proportional to the first power of the concentration of the solution, the one-half power of the flow velocity of the solution, and, inversely, the one-half power of the membrane length in the direction of the flow. In the natural convection, it is proportional to the five-quarters power of the concentration of the solution. These experimental results agree with the relation of the equations of the limiting-current density for the electrode process. The change in the relative transport numbers of ionic species with the same sign, such as the magnesium and sodium ions or the sulfate and chloride ions, with the flow velocity, the concentration, and the temperature of the solution, the dimension of the membrane in the direction of the flow, and the current density were observed. The results were explained in terms of the change in the condition of the diffusion-boundary layer.
  • Haruo Takaya, Naoyuki Todo, Tadasuke Hosoya
    1969 Volume 42 Issue 10 Pages 2748-2755
    Published: 1969
    Released: March 27, 2006
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    In acid-catalyzed reaction systems a new acidity function, T0, which is related to the first-order rate constant, k1 by the equation log k1=CT0 was defined by T0=−log (aH+/awh5h1f\ eweq) and was theoretically calculated in much the same manner as in Glueckauf’s treatments on a salt solution but with the additional assumption that the character of a hydrated univalent activated complex is represented by that of a hydrated alkali metal cation. The calculated results show that T0 in hydrochloric acid can be represented by:
    T0=2.4(3.9−h1+h5)logaw−logma.
    This equation shows that if the hydration number (the water molecules bound with an activated complex) of an activated complex, h1, increases by one, the corresponding increment of T0 becomes −2.4logaw. It was also shown that the value of fAH+fBfAfBH+ is not always constant, but depends on the hydration numbers of the AH+ and BH+ species as well as on the acid concentrations. The factors affecting the acidity function, T0, were compared with those affecting the activity of water. The applicability of the T0 was examined by means of the observed logk1 value reported by Bunnett.
  • Takeshi Takemura, Hiroaki Baba
    1969 Volume 42 Issue 10 Pages 2756-2762
    Published: 1969
    Released: March 27, 2006
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    Phosphorescence and absorption spectra, phosphorescence- and excitation-polarization, spectra and phosphorescence lifetimes were measured at 77°K for benzaldehyde, acetophenone and their eight derivatives with a halogen atom, or a hydroxyl, methoxyl or amino group as a substituent at the para position. In chloro- and bromo-derivatives, the phosphorescent triplet state is of the (n*) type, and is mixed with the 1La(π,π*) state by direct spin-orbit interaction, as in the case of the parent carbonyls. In addition, owing to the heavy-atom effect, it gains its singlet character by the mechanism
    (Remark: Graphics omitted.)
    which accounts for the observation that the phosphorescence spectrum involves out-of-plane-polarized vibrational bands. Substitution of a more electron-donating hydroxyl, methoxyl, or amino group brings about a change of the phosphorescent state from the 3(n*) state to the; 3La(π,π*). The following mechanisms are shown to be important to the 3La(π,π*) state:
    (Remark: Graphics omitted.)
    These account for two progressions with mutually perpendicular polarizations observed in the phosphorescence spectrum. The lifetimes for the transitions from the 3La(π,π*) state to the ground state of the substituted carbonyls were found to be substantially shorter than the corresponding lifetimes in aromatic hydrocarbons. This fact is quantitatively interpreted as due to the presence of a low-lying 1(n*) state.
  • Yukio Kubota, Masaji Miura
    1969 Volume 42 Issue 10 Pages 2763-2767
    Published: 1969
    Released: March 27, 2006
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    The lowest triplet state of acridine dyes has been studied by an ESR technique over a wide range of concentration and in various solvents. The ESR spectra of the triplet state have been observed at a resonance field of ca. 1550 gauss, corresponding to the ΔM=2 transitions. The ESR data characteristic of the triplet state depend on the dye concentration; this has been interpreted as being due to the association of dye molecules. The values of the zero-field splitting parameter, D*, calculated from the ΔM=2 transition spectra lead to the assignment of the lowest triplet state of acridine dyes as the (π−π*) state.
  • Tomoo Miyazaki, Hidehito Ohbayashi
    1969 Volume 42 Issue 10 Pages 2767-2772
    Published: 1969
    Released: March 27, 2006
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    The CNDO/2 method, an approximate self-consistent molecular orbital theory, has been applied to the calculation of equilibrium distances of the carbon-hydrogen bond and the normal and hypothetical carbon-carbon single or double bonds which are usually considered te-te, tri-tri, di-di and te-tri single bonds or tri-tri and di-di double bonds between carbon hybrids. The electronic interaction energies between non-adjacent atomic orbitals for sigma system considering appropriate carbon hybrids have been estimated. From the results of these calculations, it follows that the carbon-carbon bond length of sigma system is little affected by the types of hydbridization of carbon atoms.
  • Kazushige Suzuki, Sachio Matsumoto, Takehiko Watanabe, Sôzaburo ...
    1969 Volume 42 Issue 10 Pages 2773-2777
    Published: 1969
    Released: March 27, 2006
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    In order to obtain information on the dispersion state of W/O type emulsions, the steady-flow viscosity in a wide shear range has been studied using a capillary type viscometer. Emulsions prepared by using Arlacel 83 or Arlacel 60, are classified according to the kind of hydrocarbon used as the suspending fluid, i.e., benzene, cyclohexane, liquid paraffin, isopropyl myristate, and squalane systems, respectively. Although all systems show the so-called shear thinning flow, shear dependence of the viscosity is not only influenced by the disperse phase concentration and emulsifier concentration, but is also much effected by the kind of suspending fluid. Such non-Newtonian behavior is observed markedly in benzene systems. It may thus be assumed that the water droplets in benzene have a tendency to form a large aggregate not easily redispersed under shear. The formation of aggregate may be facilitated by the disturbance of the orientation of the adsorbed emulsifier molecules at the interface due to the mutual interaction between the π-electron in benzene molecule and the emulsifier molecule.
  • Kimitaka Sato, Ohiko Kammori
    1969 Volume 42 Issue 10 Pages 2778-2790
    Published: 1969
    Released: March 27, 2006
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    As it was found that metallic iron is dissolved in acetylacetone (Hacac), the interaction between the solute and the solvent in the dissolution phenomena, together with the process of the dissolution of metal, were examined in detail in order to apply it to analytical techniques. The factors of the oxygen, the co-existing water, and the dissociated proton in acetylacetone were shown to be effective in the dissolution. With typical β-diketones, the exception of acetylacetone, such as trifluoroacetylacetone (HTFA), hexafluoroacetylacetone (HHFA), benzoyltrifluoroacetone (HBTA), 2-furoyltrinuoroacetone (HFTA), and 2-thenoyltrifluoroacetone (HTTA), were also employed; they were shown to have the same properties as the above one. The relationship between the solubilities of metals and the effect of adding an organic solvent, the equilibrium reactions of fluorine-containing β-diketones with water or alcohols, or the preferred enol forms of trifluorosubstituted β-diketones, were also discussed, paying attention to the accelerating effects of the solvents on the dissolution.
  • Isao Oonishi, Fumio Muto, Yoshimichi Komiyama
    1969 Volume 42 Issue 10 Pages 2791-2796
    Published: 1969
    Released: March 27, 2006
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    The crystal structure of trans-dinitrotetramminecobalt(III) nitrate monohydrate [Co(NO2)2-(NH3)4]NO3·H2O has been determined from three dimensional X-ray diffraction data. The dimensions of orthorhombic unit cell are: a=10.02 Å, b=6.02 Å, c=16.84 Å, and Z=4. The space group is P212121. The structure has been refined by the three dimensional Fourier and least-squares method to R=0.103. The complex ion has a slightly distorted octahedral coordination with six N atoms at about 1.98 Å (two are N atoms of nitro groups and the others ammonium groups). The complexes are tightly bound together by N–H···O and O–H···O interactions, constructing a three dimensional network.
  • Tsutomu Seimiya, Hisako Kozai, Tsunetaka Sasaki
    1969 Volume 42 Issue 10 Pages 2797-2800
    Published: 1969
    Released: March 27, 2006
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    The adsorption of cobaltous ions on fine glass beads was measured for dilute aqueous 60CoCl2 solutions with pH values from 2 to 10 and with concentrations from 10−6 to 10−10 mol/l. The amount of the adsorption of cobaltous ions on glass showed a maximum at pH near 9, and it was zero at both ends of the pH region for all the initial concentrations studied. This fact is considered to confirm the theory of radiocolloid formation by the so-called adsorption method. The mechanism of radiocolloid formation was further discussed in detail. The formation of radiocolloids was explained by the adsorption of cobaltous ions on foreign particles, while the formation of insoluble cobaltous hydroxide was ruled out. It was estimated from these measurements that a very minute amount of foreign particles is sufficient to adsorb cobaltous ions and to change a large franction of the solute to radiocolloid. It was emphasized that such an estimation can be made only by the measurement of the adsorption, expressed by the unit of mol/cm2 as in the case of the present experiment, instead of the conventional unit of cpm/g or percent adsoiption.
  • Goro Yamaguchi, Mitsuko Nakano, Mamoru Tosaki
    1969 Volume 42 Issue 10 Pages 2801-2807
    Published: 1969
    Released: March 27, 2006
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    In order to clarify the influence of composition-dependent cation vacancies in defective spinels on the diffusion, the diffusion rates of Ni2+ in several kinds of defective spinels (MgO·xAl2O3, where x=1.1,1.2,1.3,1.4 and 1.5) and a perfect spinel (MgO·Al2O3) were measured by the use of an electron probe micro-analyzer, and the diffusion coefficients were obtained. The diffusion coefficients were found to be linear to the concentrations of the composition-dependent vacancies. The so-called activation energies which were calculated from the Arrhenius plot were about 70 kcal/mol for the defective spinels and 106 kcal/mol for the perfect spinel. It may be concluded that composition-dependent cation vacancies govern the diffusion of cations in the defective spinel, while temperature-dependent vacancies probably predominate in the perfect spinel.
  • Kazuhiko Ishizu, Kazuo Mukai, Hideo Hasegawa, Koichi Kubo, Hiroaki Nis ...
    1969 Volume 42 Issue 10 Pages 2808-2814
    Published: 1969
    Released: March 27, 2006
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    The electron spin resonance has been observed for the anion radicals of 4,4′-diethyl biphenyl, 4,4′-diisopropyl biphenyl, 4,4′-dicyclohexyl biphenyl, 2,2′-diethyl biphenyl, and 2,2′-diiso-propyl biphenyl. Both of the β- and γ-proton coupling constants of alkyl groups have been precisely determined, and the positive temperature dependence has been verified for the β-proton coupling constant of 4,4′-dialkyl biphenyls. The ratio (R) of β-proton coupling constant of the other alkyls to the methyl proton coupling constant has been derived, and the evidence of the restricted rotation has been widely established for each derivative based on the angular dependence of the β-proton coupling constant, which can be expressed as follows:
    aiβπ<Q>, Q=B0+Bcos2θ
    The minimum R value obtained for 2,2′-diethyl biphenyl enabled us to assume that a rotation of the alkyl group would be tightly locked at the ortho position. The R value of 2,2′-diisopropyl biphenyl revealed that the isopropyl β-proton would lie on the biphenyl aromatic plane. The anomalous R values associated with the ortho-alkylated biphenyls can be well understood as resulting from the facts that anion radicals have a more dominant character than do neutral molecules to reduce a twisting angle between the two phenyls, and that the free rotation of the alkyl group is strongly restrained by the steric hindrance between the alkyl group and the closely-oriented ortho-ring proton.
  • Takako Shinoda
    1969 Volume 42 Issue 10 Pages 2815-2820
    Published: 1969
    Released: March 27, 2006
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    A theoretical vapor pressure equation of the form logP+(3⁄2)logT=a+bT for a diatomic molecule was applied to carbon monoxide in condensed phases. The two parameters in the equation determined from experimental vapor pressure data were used to obtain values of the static lattice energy E0, the zero point energy Ez, the geometric mean frequency ωg and the mean frequency of molecular rotation ωR in the respective phases by the information of lattice vibrations at low temperatures. From the mean values of molecular rotation frequencies, the hights of the potential barrier for hindered rotations were estimated to be 360, 230±10 and 110 cal/mol respectively.
  • Takeaki Iida, Hiroshi Nozaki
    1969 Volume 42 Issue 10 Pages 2820-2827
    Published: 1969
    Released: March 27, 2006
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    The electrophotographic properties of titanium dioxide-polymer dispersion layers were studied. The titanium dioxide powder of the rutile type and three well-known polymers, polyvinyl acetate, polyvinyl chloride, and polystyrene, were used. The measurements were done on the corona-charging properties, e. g., the resistivity and the capacitance of the layer, the rising gradient of the surface potential, and the fatigue effect of pre-illumination. The results make it clear that the analysis of an equivalent circuit can be applied to the interpretation of the rising gradient of the surface potential and to that of the dark decay to some extent. Moreover, it is found that the logarithm of the potential of the dark decay decreases proportionally to the cube root of the time at the initial step, while, at the next following step, it decays proportionally to the square root of the time. The mechanism of the dark decay of the surface potential is also discussed.
  • Kozo Tsuji, Seizo Okamura
    1969 Volume 42 Issue 10 Pages 2827-2830
    Published: 1969
    Released: March 27, 2006
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    Radical conversions in γ-irradiated 3-methylpentane-isobutene systems were observed by means of the electron spin resonance method after keeping the sample at −196°C for a few days, or by subjecting it to ultraviolet irradiation. One of the changes was caused by hydrogen atom abstraction from neighboring molecules by original free radicals. The other change was attributed to dissociation of the free radicals from 3-methylpentane by ultraviolet irradiation.
  • Yoshihiko Kanchiku
    1969 Volume 42 Issue 10 Pages 2831-2835
    Published: 1969
    Released: March 27, 2006
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    The chemical behavior of TcCl62− in HCl solutions of different concentrations has been investigated. It was confirmed that TcCl62− is sensitive to ultraviolet and visual light, giving a series of aquated species the quantities of which depend on the HCl concentration. Those technetium(IV) chlorocomplexes were isolated by means of ion-exchange and paper electro-phoresis, and the composition of each species was determined by measuring the Cl/Tc ratio and the charge per species. The absorption spectra of isolated species were also measured.
  • Akira Uehara, Eishin Kyuno, Ryokichi Tsuchiya
    1969 Volume 42 Issue 10 Pages 2835-2840
    Published: 1969
    Released: March 27, 2006
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    The following chromium (III) complexes with the β-aminoethylsulfonic-N,N-diacetic acid (AEDA) and aspartic-N,N-diacetic acid (ASDA) were newly prepared; K3[Cr(aeda)2]·4H2O (pale red) (I), [Cr(OH)(Haeda)(o-phen)]·2H2O (orange) (II) and [Cr(Hasda)(H2O)2]·H2O (reddish purple) (III). From the results of spectral measurments, it was found that AEDA acts as a quadridentate ligand as well as a terdentate one in an aqueous solution, but only as a terdentate ligand in a crystal state, and that the coordinating ability of the oxygen atom of sulfonic radical in AEDA is weaker than that of carboxylic radical in ammoniapropionicdiacetic acid (APDA). In Complex III, ASDA behaved as a quadridentate ligand rather than as a quinquedentate. Complexes II and III showed some interesting thermal decomposition processes. The former lost one mole of water at 110°C from the hydrogen atom in free sulfonic acid radical and the coordinated OH group, accompanied with the increase of coordination number of AEDA from 3 to 4. In the latter, one mole of crystalline water was lost first, and then the carboxylic acid bound to the methylene group at β-position in the ligand was decomposed to liberate carbon dioxide, and the coordinated asda was changed into apda.
  • Masaru Kimura
    1969 Volume 42 Issue 10 Pages 2841-2843
    Published: 1969
    Released: March 27, 2006
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    The kinetics of the ligand-substitution reactions of the nitrilotriacetatoniccolate(II) complexes with trans-1,2-cyclohexanediaminetetraacetate (CyDTA) ions were studied polarographically from pH 4.8 to 5.8 at an ionic strength of 0.2 and at 25°C. The reactions were found to proceed only through the dissociation reactions of the nitrilotriacetatoniccolate(II) complexes. The rate constants of the dissociation reactions were also determined. In contrast to the reactions of the same complex with ethylenediaminetetraacetate (EDTA) ions and N-2-hydroxyethylene-diaminetriacetate (HEDTA) ions, there were no direct reactions of the nitrilotriacetatoniccolate-(II) complexes with CyDTA ions. The reaction was of the first order in respect to the concentration of the nickel-complex and independent of the CyDTA concentration; the reaction of the complex with CyDTA ions was found to have the different mechanisms from the similar reaction with EDTA and HEDTA, and to be due to the steric effect of the cyclohexane ring in the CyDTA molecule.
  • Masaru Kimura
    1969 Volume 42 Issue 10 Pages 2844-2848
    Published: 1969
    Released: March 27, 2006
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    The kinetics of the reactions of nickel(II)-nitrilo(diacetic)propionate (NDAP) and nickel(II)-nitrilo(diacetic)isopropionate (NDAIP) complexes with ethylenediaminetetraacetate (EDTA) ions, and those of the nickel (II)-taurin-N-diacetate (TDA) complex with EDTA and trans-1,2-cyclohexanediaminetetraacetate (CyDTA) ions, have been studied polarographically in solutions with pH 4.8–6.0 at 25°C and at an ionic strength of 0.2. All the reactions except those with CyDTA proceeded through four reaction paths, and the rate constants for the reaction paths were determined. The reaction of the nickel(II)-TDA complex with CyDTA was found to proceed only through the complete dissociation of the Ni(II)-TDA complex. There was not a direct reaction of the complex with CyDTA. Consequently, the overall reaction with CyDTA became much slower than that of the same complex with EDTA. The rate constants obtained were compared with those of the similar reactions of the nickel (II)-nitrilotriacetate (NTA) complex with EDTA and CyTDA which had been reported previously. The rate of the dissociation reaction of nickel(II) complexes increased in the order: NDAIP≤NDAP<NTA<TDA. Especially, the rate of the Ni(II)-TDA complex was about 30 times that of Ni(II)-NTA complex.
  • Hideo Sato, Ryokichi Tarao, Hiromi Higashi
    1969 Volume 42 Issue 10 Pages 2849-2853
    Published: 1969
    Released: March 27, 2006
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    The proton magnetic resonance and infrared spectra of the mixtures of dialkylaluminum 2-aminoethoxide (AlR2OCH2CH2NR′2)2 and trialkylaluminum (AlR″3)2 were measured. Special attention was paid to the infrared frequencies of the NH2 stretching and scissors bands and to the chemical shifts of the methyl groups attached to the aluminum and nitrogen atoms. From the results it was concluded that (AlR″3)2 reacts with (AlR2OCH2CH2NR′2)2 to form a 1:1 coordination compound AlR2OCH2CH2NR′2→AlR″3 quantitatively. At the same time, the redistribution and exchange reactions of the alkyl groups were observed.
  • Nobuyuki Tanaka, Kenzo Nagase
    1969 Volume 42 Issue 10 Pages 2854-2857
    Published: 1969
    Released: March 27, 2006
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    The thermal decomposition reactions of [Cr(NH3)6]Cl3, [CrCl(NH3)5]Cl2 and cis-[CrCl2-(NH3)4]Cl in solid state were studied by the manometric, infrared spectroscopic and reflectance spectroscopic methods. The decomposition of these complexes in vacuum was initiated by substitution of an outer-sphere chloride ion for a coordinated ammonia. The rate constants, activation energies and activation entropies of these substitution reactions were obtained and the possible reaction processes were discussed. The products cis,cis-[CrCl3(NH3)3] and cis,trans-[CrCl3(NH3)3] were obtained on the heating of cis-[CrCl2(NH3)4]Cl.
  • Motonori Tamaki, Isao Masuda, Koichiro Shinra
    1969 Volume 42 Issue 10 Pages 2858-2862
    Published: 1969
    Released: March 27, 2006
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    Square, planar bis(acetylacetone)-, and bis(benzoylacetone)-etylenediimine-Co(II) chelates with a low-spin d7 electron structure yield nitrosyl complexes with the chelate : NO molar ratio of 1 : 1. On the basis of the IR spectra and the NMR spectra, and on the basis of molecular-weight determinations, these nitrosyls have been considered as being penta-coordinate cobalt complexes with square-pyramidal configuration. The nitrosyls are diamagnetic, indicating an electron-pairing bond between the central Co(II) and the NO molecule. The NO groups in these nitrosyls have been postulated to be predominantly neutral. In the electronic spectra, these penta-coordinate, diamagnetic Co(II) complexes show a characteristic absorption band at 18–20×103 cm−1 with logε\doteqdot3.
  • Haruko Ito, Junnosuke Fujita, Kazuo Saito
    1969 Volume 42 Issue 10 Pages 2863-2869
    Published: 1969
    Released: March 27, 2006
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    Absorption (AB) spectra of dichloro(l-tetrahydrogenpropylenediaminetetraacetato)platinum-(II) and palladium(II) and dichloro(d-hydrogendiaminopropionato)platinum(II) and palladium(II) were interpreted on the basis of a comparison of their circular dichroism (CD) spectra with those of dichloro(l-propylenediamine)platinum(II) and palladium(II). The d-d bands of edtaH4 and l-pdtaH4 complexes shifted to longer wavelength as compared with those of l-pn complexes. The shift was discussed, based on the effects of the weaker ligand field strength and apical interaction of the acetato groups of these ligands.
  • Shin Tsuge, Tadaoki Okumoto, Tsugio Takeuchi
    1969 Volume 42 Issue 10 Pages 2870-2873
    Published: 1969
    Released: March 27, 2006
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    A new, simple and rapid method for determining chlorine in chlorine-containing polymers was investigated by means of pyrolysis-gas chromatography. Hydrogen chloride evolved during the thermal degradation of the polymers was eliminated by a NaOH precut column, and only the organic compounds sensitive to flame ionization detector were separated to record the pyrograms. Chlorine content of the polymers was calculated from the relative yield of the degradation products using a theoretical equation deduced from the degradation mechanisms of the polymers. This unique method permits very rapid determination of chlorine with the use of about 0.1 mg of the sample without either the use of calibration curves or weighing of the samples.
  • Hiroyasu Ichikawa, Muraji Shibata
    1969 Volume 42 Issue 10 Pages 2873-2877
    Published: 1969
    Released: March 27, 2006
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    Three new tervalent dinitro complexes of cobalt(III) have been prepared by the use of a tricarbonatocobaltate(III) solution or a similar solution as the starting material. These complexes, [Co(NO2)2(CO3)3]3−, [Co(NO2)2(OX)2]3− and [Co(NO2)2CO3OX]3− are characterized by their absorption spectra in solution. The geometrical structures of these complexes have been determined as of the cis-form on the basis of their IR spectra. The compounds were not stable against decomposition in aqueous solutions: the bis(oxalato) compound was most unstable against the decomposition to the Co(II) state. The stability has been discussed in connection with the specific absorption band of the coordinated NO2 ligand.
  • R. C. Aggarwal, S. K. Singh
    1969 Volume 42 Issue 10 Pages 2878-2881
    Published: 1969
    Released: March 27, 2006
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    Titanium tetrafluoride reacts with benzaldehyde phenylhydrazone to yield 1:1 adduct and with benzophenone phenylhydrazone 1:2 as well as 2:1 adducts, while other tetrahalides form 1:1 adducts with both the phenylhydrazones. All these complexes are coloured and stable at room temperature. The infrared spectral studies of phenylhydrazones and their titanium (IV) complexes have been made in the 4000–200 cm−1 region.
  • Yoshio Iwakura, Keikichi Uno, Tatsuhiko Hongu
    1969 Volume 42 Issue 10 Pages 2882-2885
    Published: 1969
    Released: March 27, 2006
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    1,3-Dipolar cycloaddition reaction of aldonitrones such as C-2-furyl-N-phenyl-, C,N-diphenyl-, and C-2-thienyl-N-phenylnitrone with N-phenylmaleimide was carried out. The product was separated into two stereo isomers, cis and trans isoxazolidines with respect to H3 and H4, which were identified by NMR spectra. Spin-spin coupling of protons on C3 and C4 of isoxazolidine ring was found to be 8.4–9.0 cps for cis isomers and to be zero for trans isomers.
  • Masuo Funabashi, Masaharu Iwakawa, Juji Yoshimura
    1969 Volume 42 Issue 10 Pages 2885-2894
    Published: 1969
    Released: March 27, 2006
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    The proposed structures of the dimeric products obtained from aliphatic aldehydes and arylamines were reexamined by IR and NMR spectra. The 1,2,3,4-tetrahydroquinoline structure was ascertained in the case of acetaldehyde or propionaldehyde, and aldolic structure was confirmed in the case of n-butyraldehyde. It was observed that the latter readily isomerizes to the former type in the presence of acetic acid. Conformational analysis of a racemic pair of the former (IIIa–c: 2,4-disubstituted, IIId- 2,3,4-trisubstituted) indicated that two isomers of IIIa–c (one has 2-equatorial, 4-quasi-equatorial and the other 2-equatorial, 4-quasi-axial substituents) have a flattened half-chair conformation and two isomers of Hid (one has 2,3-diequatorial, 4-quasi-equatorial, and the other 2-equatorial, 3-axial, 4-quasi-axial substituents) have a more remarkably flattened half-chair, i. e. a nearly plane structure. The acylation of ring nitrogen enhanced this tendency, and one of the 1-acetyl derivatives of III was deduced to have a twist half-boat conformation.
  • Waichiro Tagaki, Takehiko Kurusu, Shigeru Oae
    1969 Volume 42 Issue 10 Pages 2894-2898
    Published: 1969
    Released: March 27, 2006
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    The reaction of p-nitrophenyl benzenesulfonates has been investigated in dioxane-water solvent. The overall rate constant, kA, was separated into two composite rate constants, kAr, and kSO2, corresponding to the cleavage of C–O and S–O bonds respectively. The reactivities of hydroxide and thiophenoxide in this reaction were compared. The overall rate constant was found to be several times larger with OH than with PhS. The reactivity of OH was largely due to its higher reactivity toward sulfur, while its reactivity toward carbon atom was comparable to that of PhS. Substituent effect of the nucleophile, thiophenoxide and of the substrate shed some light on the mechanism of this reaction.
  • Shigeru Oae, Yoichiro Yoshikawa, Waichiro Tagaki
    1969 Volume 42 Issue 10 Pages 2899-2903
    Published: 1969
    Released: March 27, 2006
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    The alkaline hydrolysis of substituted phenyl benzenethiolsulfinates has been kinetically investigated. The rates were correlated with the second order kinetic equation, first order with respect to each of the hydroxide and the ester concentration. The second order rate constant for the unsubstituted ester was found to be 3.17×103 l/mol sec (water, 30°C). The Hammett ρ values were found to be ρX,Y=H=2.4 and ρY,X=H=1.6 for (Remark: Graphics omitted.) respectively.
  • Shigeru Oae, Ryuichi Nomura, Yoichiro Yoshikawa, Waichiro Tagaki
    1969 Volume 42 Issue 10 Pages 2903-2906
    Published: 1969
    Released: March 27, 2006
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    The alkaline hydrolysis of substituted phenyl benzenethiolsulfonates has been investigated. The rate was found to be first order with respect to both hydroxide and ester. The second order rate constant for the unsubstituted ester was found to be 3.2×103 M−1 sec−1 (water 45°C). The Hammett ρ values were found to be ρX,Y=H=2.1 and ρY,X=H=1−1 for (Remark: Graphics omitted.) respectively. The reactivities of three esters, i. e. phenyl benzenethiolsulfonate, -thiolsulfonate and -sulfonate were compared.
  • Ko Taki
    1969 Volume 42 Issue 10 Pages 2906-2911
    Published: 1969
    Released: March 27, 2006
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    The reactive species produced by the explosion of silver acetylide were found to react with hydrocarbon and to give acetylene and ethylene as the main products. The reactive species must be carbon oligomers. Since, in the reactions with higher hydrocarbons, acetylene and ethylene are also produced, their formation process may be the decomposition of the adduct of the reactive species. From the product distributions, the phase dependence of the ratio of ethylene to acetylene, and the effect of such moderator as carbon dioxide and inert gas, the reactive species are considered to be not only the monoatomic carbon (C1) but also the diatomic carbon (C2). The effect of a NO radical scavenger in the reactions of both ethane and propane is also described.
  • Tsutomu Kagiya, K\={o}z\={o} Narita
    1969 Volume 42 Issue 10 Pages 2912-2917
    Published: 1969
    Released: March 27, 2006
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    The catalytic activities of various acids, bases, and salts in formaldehyde polymerization in a liquid carbon dioxide solution were studied in connection with the structures of the catalysts. The activity of the catalysts increased with decreases in the pKa of Brönsted acids and in the ion-dissociation energy of alkyl acetates, and with increases in the pKa′ of organic compounds containing a nitrogen or oxygen atom, such as triethylamine or diethyl ether, and in the pKa of the conjugated acids of sodium salts. The activity of the salts obtained from a strong acid with various bases increased with a decrease in the pKa′ of the bases, while that of the salts from weak acids with weak bases decreased with an increase in the summation of the pKa values of acids and the pKa′ values of bases, reaching a minimum point and then increasing. The activity of various salts decreased with an increase in the pH in an aqueous solution, reached a minimum point at pH 6, then increased.
  • Mamoru Nakai, Naomichi Furukawa, Shigeru Oae
    1969 Volume 42 Issue 10 Pages 2917-2920
    Published: 1969
    Released: March 27, 2006
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    N,N-Dichlorocyclohexylamine-1-14C has been treated with sodium methoxide in methanol and then with hydrochloric acid to yield 14C-labeled 2-aminocyclohexanone hydrochloride. Successive degradations have revealed that practically all the 14C activity was found in the carbonyl carbon of the original aminoketone. From the 14C distribution, it has been concluded that the reaction is essentially the same as that proposed for the Neber rearrangement. As a part of the degradation of 2-aminocyclohexanone, deaminative diazotization was employed to obtain cyclopentanecarboxylic acid together with other minor products. The 14C tracer work revealed that the carbonyl group of the acid is originated from the carbonyl group of the 2-amino-ketone.
  • Sohei Suga, Hiromitsu Masada, Haruki Suda, Yoshihisa Watanabe, Yoshino ...
    1969 Volume 42 Issue 10 Pages 2920-2924
    Published: 1969
    Released: March 27, 2006
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    Ethyl vinylacetate and ethyl crotonate reacted with cobalt hydrocarbonyl at 25°C to give three isomeric acylcobalt carbonyls, α- and γ-carbethoxy-butyrylcobalt carbonyls and β-carbethoxy-iso-butyrylcobalt carbonyl. The distribution of these complexes depends greatly on the reaction time (0.5–20 hr). In both cases the β-isomer predominates at shorter reaction times (0.5–1.5 hr), while the γ-isomer predominates at longer reaction times. This shows that isomerization occurs among the complexes and that the equilibrium is very favorable to the γ-isomer. Acrylates and styrene react with cobalt hydrocarbonyl to give two isomeric acylcobalt carbonyls. The isomerization of the acylcobalt complex with a branched structure to that with a straight-chain structure is much promoted by the phenyl and ester groups. The promoting effect of the ester groups is the highest in benzyl, followed by allyl, and ethyl, isopropyl, butyl, and cyclohexyl. Such a promoting effect can reasonably be attributed to the −I effect of these groups.
  • Ko Wakabayashi, Masaru Tsunoda, Yasushi Suzuki
    1969 Volume 42 Issue 10 Pages 2924-2930
    Published: 1969
    Released: March 27, 2006
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    2-Substituted 4,6-bis(trichloromethyl)-s-triazines have been prepared by the cotrimerization of CCl3CN with some nitriles. The reaction proceeds, in general, smoothly at ordinary pressure in the presence of hydrogen halide or Friedel-Crafts catalyst-hydrogen halide complex. An improved method was developed for the nitriles such as propionitrile with which CCl3CN did not easily cotrimerize under above mentioned conditions.
  • Ko Wakabayashi, Masaru Tsunoda, Yasushi Suzuki
    1969 Volume 42 Issue 10 Pages 2931-2937
    Published: 1969
    Released: March 27, 2006
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    2-Substituted thio-4,6-bis(trichloromethyl)-s-triazmes, a new class of s-triazine derivatives, were obtained by the cotrimerization of CCl3CN with a wide variety of thiocyanates. Generally, the reaction proceeded smoothly at ordinary pressure in the presence of hydrogen chloride or the combined catalyst, Friedel-Crafts catalyst-hydrogen chloride.
  • Matsuji Takebayashi, Toshikazu Ibata, Hideki Kohara, Kozaburo Ueda
    1969 Volume 42 Issue 10 Pages 2938-2944
    Published: 1969
    Released: March 27, 2006
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    The reaction of α-diazoacetophenone with olefinic compounds, such as vinyl acetate, cis- and trans-stilbenes and cyclohexene, has been studied in the presence of bis(acetylacetonato)copper-(II). The reaction gave the corresponding cyclopropane derivatives, the addition products of benzoylcarbene to the double bond of olefinic compounds in good yields, accompanied by cis-and trans-dibenzoylethylenes, dibenzoylethane or dilactone. Addition of carbene was found to be stereospecific in the cases of cis- and trans-stilbenes. A mechanism has been advanced in which a ketocarbene-metal chelate complex is included as an intermediate of the reaction.
  • Michinori Oki, Isao Oka, Katsushiro Sakaguchi
    1969 Volume 42 Issue 10 Pages 2944-2947
    Published: 1969
    Released: March 27, 2006
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    The infrared S=O stretching absorptions of several simple sulfoxides have been measured. Some sulfoxides show one absorption maximum, whereas others show two. These results may be attributed to the rotational isomerism about the S–C axis. Convincing evidence for this conclusion has been obtained by the measurement of the spectra of methyl isopropyl sulfoxide at various temperatures.
  • Motoo Muroi, Yuzo Inouye, Minoru Ohno
    1969 Volume 42 Issue 10 Pages 2948-2951
    Published: 1969
    Released: March 27, 2006
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    A partial asymmetric synthesis was achieved in the carbon-carbon condensation which involved the reaction of (−)-menthyl pyruvate with trimethyl phosphite, followed by alkaline hydrolysis of the intermediate cyclic oxyphosphorane to yield (−)-(S:S)-2,3-dimethyltartaric acid. With knowledge of absolute configurations of both the chiral center and the predominant enantiomer of the product, an ex post facto interpretation of the steric course was made on the basis of relative steric stability of transition state conformations of the addition step of III to I.
  • Takeo Sakan, Kousuke Kusuda, Toshio Miwa
    1969 Volume 42 Issue 10 Pages 2952-2956
    Published: 1969
    Released: March 27, 2006
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    The alkaline hydrogen peroxide oxidation of compound A, C17H14O5N2, a base-catalyzed condensation product of o-nitroacetophenone, gave a dehydro compound, C17H12O5N2. The structure of the dehydro compound was deduced from the spectral data of its derivatives to be a (o-nitrobenzoyl)-1-hydroxycarbostyril. The forced hydrogenation of the dehydro compound gave 3-(o-aminobenzoyl)-4-methylcarbostyril, which was synthesized by the condensation of o-aminoacetophenone and ethyl o-nitrobenzoylacetate followed by reduction. Therefore, the dehydro compound proved to be 1-hydroxy-4-methyl-3-(o-nitrobenzoyl)carbostyril. On the other hand, the alkaline hydrogen peroxide oxidation of compound A methyl ether gave o-nitrobenzoic acid and 1-methoxy-3-methyldioxindole along with o-nitroacetophenone. These facts are explained by assuming a transition state which would be controlled by the presence of a hydrogen bonding.
  • Yoshiaki Ohgo, Juji Yoshimura, Masami Kono, Tetsuo Sato
    1969 Volume 42 Issue 10 Pages 2957-2961
    Published: 1969
    Released: March 27, 2006
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    Stereoselectivity has been investigated in addition reactions of 2,3-O-isopropylidene-D-glyceraldehyde (I) or 2,3-di-O-benzyl-D-glyceraldehyde (II) with phenylmagnesium bromide or phenyllithium. Stereoselectivity difference between the Grignard and phenyllithium reactions occurred in the case of compound (I): the phenyllithium reaction gives threo and the Grignard reaction erythro products predominantly. On the other hand, no difference in stereoselectivity has been observed between the reactions with 2,3-di-O-benzyl-D-glyceraldehyde (II): both reactions gave threo product predominantly.
  • Seiji Usami, Takayoshi Kondo, Kotaro Nishimura, Yuzo Koga
    1969 Volume 42 Issue 10 Pages 2961-2965
    Published: 1969
    Released: March 27, 2006
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    A novel method of synthesizing cobalt carbonyl was investigated by using noble metal catalysts. It has been observed that the materials containing palladium, i. e., palladium black, palladium chloride, palladium acetylacetonate, bistriphenylphosphine dichloropalladium, and palladium-on-carriers, have a catalytic effect on the cobalt carbonylation reaction, and that palladium-on-carbon (Pd-C) is the most active catalyst. The reactivity of cobalt compounds in the cobalt carbonylation reaction catalyzed by noble metals increases in this order: CoSO4<<CoO\lesssimCo(OAc)2\lesssimCo-oleate<Co(OH)2. When the Pd-C catalyst is used, cobalt hydroxide reacts with synthesis gas of 150 kg/cm2 to give cobalt carbonyl almost quantitatively, even at from 50 to 55°C. The catalytic activities of noble metals were shown to be, in the order of decreasing activity: Pd>Au>Pt>>Ag. The effect of the catalyst concentration and the activity of noble-metal catalysts were also compared with those in the case of dicobalt octacarbonyl, as an autocatalyst.
  • Seiji Usami, Kotaro Nishimura, Takeo Koyama, Saburo Fukushi
    1969 Volume 42 Issue 10 Pages 2966-2970
    Published: 1969
    Released: March 27, 2006
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    The reaction conditions of cobalt carbonylation catalyzed by palladium have been investigated. Polar solvents have, with some exceptions, been shown to be superior to nonpolar solvents. The fact that the total pressure of synthesis gas and the partial pressure of hydrogen, especially the latter, have a great effect on the initiation temperature of reaction suggests that the presence of hydrogen is very important in the present reaction. The low reactivity and poor yield in the reactions of Raney cobalt indicate that a low-valency intermediate in the course of the cobalt-carbonylation reaction of cobaltous compounds may be somewhat different from the Raney-type Co(0). The initial step of the reaction seems to be affected only a little by various additives e. g., water, triphenyl phosphine, lead naphthenate, and sodium hydroxide. The data previously available suggest that a palladium catalyst may primarily promote the reduction of Co (II) to Co(0) by activating hydrogen. The test of the lifetime of a palladium-on-carbon catalyst for a month indicates that there is no apparent decrease in the catalytic activity within this period.
  • Teruo Matsuura, Katsuyuki Ogura
    1969 Volume 42 Issue 10 Pages 2970-2972
    Published: 1969
    Released: March 27, 2006
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    The photochemistry of a quinone methide (Ia) was investigated. Ia was unchanged on photolysis of an alcoholic solution (0.0064 M) with a high-pressure mercury lamp (Pyrex filter). However irradiation of a highly dilute solution of Ia or a sensitized reaction (acetophenone) gave an alcohol adduct (IIe in methanol and IIf in isopropyl alcohol) which might be formed via triplet excited state(s) of Ia. The methanol adduct IIe was also formed by the irradiation of Ia in methanol with a low-pressure mercury lamp through quartz. In this case the formation of He appears to be initiated by photochemical decomposition of methanol.
  • Teruo Matsuura, Isao Saito
    1969 Volume 42 Issue 10 Pages 2973-2975
    Published: 1969
    Released: March 27, 2006
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    In connection with the photodynamic action of the biological systems, photosensitized oxygenation of a thiazole was investigated. Photooxidation of 2,4,5-triphenylthiazole in methanol in the presence of rose bengal resulted in the formation of benzil and benzamide. On the other hand, photooxidation of 2,4,5-triphenylthiazole in chloroform containing methylene blue as a sensitizer gave N,N-dibenzoylthiobenzamide in good yield. Possible mechanisms for these reactions, involving an endo-peroxide or a zwitterionic peroxide, are discussed.
  • Iwao Ojima, Kin-ya Akiba, Naoki Inamoto
    1969 Volume 42 Issue 10 Pages 2975-2981
    Published: 1969
    Released: March 27, 2006
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    N-Substituted thiocarbamoyldiarylphosphine oxides and sulfides were prepared by the addition reaction of diarylphosphine oxides and diphenylphosphine sulfide with isothiocyanates. Diarylphosphine oxides and diphenylphosphine reacted with ammonium thiocyanate under hydrogen chloride stream to produce diarylphosphinyl- and diarylthiophosphinyl-substituted bis(iminomethyl) sulfides, which are a new type of sulfide. Diphenylphosphine also reacted with thiocyanic acid in ether to give thiocarbamoyldiphenylphosphine and bis(diphenylphosphinyliminomethyl) sulfide. Mechanisms for formation of these bis(iminomethyl) sulfides have been discussed.
  • Taiichi Okada, Mituyosi Kawanisi, Hitoshi Nozaki
    1969 Volume 42 Issue 10 Pages 2981-2983
    Published: 1969
    Released: March 27, 2006
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    Irradiation of aromatic oxime benzoates, R1R2C=N–OCOPh, in benzene solution gives the corresponding azines, (R1R2C=N–)2, and ketones, R1R2C=O, along with PhCO2NH4. PhCO2H and Ph2 are also obtained in all cases. The reaction course can be explained by assuming a radical fission of excited R1R2C=N–OCOPh which gives radicals R1R2C=N· and ·OCOPh in the initial step. Sensitization experiment establishes the fact that a triplet state of the oxime benzoate is involved as a chemically reactive species.
  • Yoshihiro Sugi, Sekio Mitsui
    1969 Volume 42 Issue 10 Pages 2984-2989
    Published: 1969
    Released: March 27, 2006
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    In order to obtain further information about the catalytic hydrogenolysis of benzyl-type compounds, the hydrogenolysis of optically active 2-methyl-2-phenylaziridine (I) over several group VIII transition metal catalysts was investigated in ethanol under ordinary pressure and at room temperature. 2-Phenylpropylamine (II) was obtained as the main product over all the catalysts. The configuration of II was inverted over the palladium catalyst. However, the hydrogenolysis over the platinum catalyst occurred with a significant retention of the configuration. Further, in the case of Raney nickel and Raney cobalt catalysts, the configurations of II were retained with the low stereoselectivities, and a small amount of 2-phenyl-2-propylamine (III) was also produced in addition to II. These results are attributable to the free-energy difference at the transition states to form π-benzyl intermediates, which depends on the affinity of these metals for the nitrogen lone-pair, the catalyst hindrance, and other factors. The SN2-type reaction is favored over the palladium catalyst. On the other hand, the SNi-type reaction is favored over platinum, Raney nickel, and Raney cobalt catalysts, where the radical-cleavage reaction will participate in addition to the SNi-type reaction over the latter two catalysts. The differences in behavior between styrene imines and styrene oxides on the catalyst surface were also discussed.
  • Akira Uchida, Satoshi Saito, Sumio Matsuda
    1969 Volume 42 Issue 10 Pages 2989-2991
    Published: 1969
    Released: March 27, 2006
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  • D. P. Nabar, S. V. Sunthankar
    1969 Volume 42 Issue 10 Pages 2991-2993
    Published: 1969
    Released: March 27, 2006
    JOURNALS FREE ACCESS
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