Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 43 , Issue 10
Showing 1-50 articles out of 87 articles from the selected issue
  • Harjoto Djojosubroto, Yoshié Tanizaki, Toshihiko Hoshi
    1970 Volume 43 Issue 10 Pages 3025-3028
    Published: 1970
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    A qualitative dichroism analysis has been made on chemical species produced from iodine in stretched sheets of polyvinyl alcohol. The absorption bands at 290 mμ and 360 mμ have been attributed to the bent triiodine ion, and the transition moments of these bands have been found to be parallel to each other. From the optical density ratio (Rd) curve, the presence of a hidden band at about 420 mμ has been pointed out, and the band has been assigned to the absorption by the linear triiodide ion. Three different chemical species are absorbed in the visible region. By comparing the Rd values, the numbers of iodine atoms in the respective species have been estimated.
  • Hiroko Yamabe, Teijiro Yonezawa, Hiroshi Kato
    1970 Volume 43 Issue 10 Pages 3029-3033
    Published: 1970
    Released: March 27, 2006
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    The relationship between the pKa value and the change in the electronic energy, ΔE, in the course of the dissociation, and the electronic structure of various mono-carboxylic acids and several azine compounds are discussed on the basis of the calculation by Hückel methods for σ and π electron systems. The parallelism between the pKa and the calculated ΔE of the acids is observed. The σ electron densities of the –COOH proton and the O lone pair, which is constituted by the released electron on the dissociation, run parallel with the pka′s. The delocalizability of the lone pair for the electrophilic reaction, and that of the proton for the nucleophilic reaction, have a linear relationship with the pka′s. Similar relations are seen in several azine compounds. Therefore, it may be said that the protonation will take place by means of the electrophilic attack at the lone pair, and that the deprotonation occurs by means of the nucleophilic attack at the proton.
  • Noriyuki Watanabe, Eiji Niki
    1970 Volume 43 Issue 10 Pages 3034-3036
    Published: 1970
    Released: March 27, 2006
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    Substituent effect of triethyltin phenyl derivatives was investigated by means of the 119Sn Mössbauer effect. The isomer shifts obtained for these compounds fall into the range −0.15–−0.18 mm/sec with respect to Pd119mSn source. p-Cl and m-Cl derivatives show broadened spectra, which may be ascribed to an unresolved quadrupole splitting. This small quadrupole interaction may be interpreted in terms of the partial ionicity of the bond formed between tin and carbon in phenyl group.
  • Osamu Kiyohara, Kiyoshi Arakawa
    1970 Volume 43 Issue 10 Pages 3037-3043
    Published: 1970
    Released: March 27, 2006
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    The sound velocity and density of binary mixtures of benzene, toluene, p-xylene and cyclohexane with 1,2-dichloroethane (DCE) as a common component were measured at temperature 20–40°C, and the excess molar volume and excess compressibility of these systems were calculated. They were found to be positive. The excess compressibility is independent of temperature in the DCE-benzene system. Thermodynamical properties and the nature of intermolecular interaction in the systems were discussed. It has been shown that there is a certain weak attraction between DCE and aromatic molecules, and that there is no complex formation viz., hydrogenbonding or change transfer complex. It has been proposed that the interaction between gauche form of DCE and aromatic molecules is of electrostatic nature (dipole-induced dipole or hyperpolarizability).
  • Takeo Mitsui, Yasuhiko Machida, Fuminori Harusawa
    1970 Volume 43 Issue 10 Pages 3044-3048
    Published: 1970
    Released: March 27, 2006
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    Recently, the PIT (phase-inversion-temperature) system was originated and developed by Shinoda and his collaborators as a guide to surfactant selection. In order to apply the PIT system to the cosmetic field, the effects of various factors on the PIT have been reinvestigated using cosmetic materials. POE alkyl ethers, whose distribution of EO chain lengths is broad, are widely used in cosmetics. In such a case, the effect of the distribution of the EO chain lengths is important. When a surfactant with a distribution of EO chain lengths was used, the PIT was lowered by an increase in the concentration of the surfactant, but when a monodisperse surfactant without any distribution was used, the PIT scarcely varied with the concentration of the surfactant. In the case of the surfactant with a distribution of EO chain lengths, however, if the ratio of oil to surfactant was kept constant, the PIT scarcely varied with the ratio of oil phase to water phase. This relationship can be used in estimating the PIT in the case of the practical production of an emulsion.
  • Kiyoshi Arakawa, Katsutaka Sasaki
    1970 Volume 43 Issue 10 Pages 3048-3053
    Published: 1970
    Released: March 27, 2006
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    Taking into account the cooperative nature of cluster formation, we applied the order-disorder theory, using Bragg and Williams’s approximation, to liquid water based on a two state model. The two state model consists of hydrogen-bonded molecules arrayed on α-sites in a tetragonal lattice and non hydrogen-bonded molecules on β-sites in the lattice. A partition function was formulated and calculated. The calculated energy difference, ε, between the molecules on β-sites and those on α-sites decreased continuously with the rise of temperature. Thermodynamic variables of liquid water were calculated at each temperature, where no adjustable parameter was used. Agreement between calculated values and observed ones is fairly good.
  • Hirofumi Okabayashi, Rume Sakai, Toshizo Isemura
    1970 Volume 43 Issue 10 Pages 3054-3063
    Published: 1970
    Released: March 27, 2006
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    The nuclear magnetic resonance spectra of the copolymers of L-proline with γ-benzyl-L-glutamate were measured in tetradeuteroacetic acid, deuterochloroform, a mixed solvent (CD3-COOD : CDCl3=4 : 1), and trifluoroacetic acid. The time dependence of the α-CH resonance peaks of copoly-(3 : 1)-(L-proline, γ-benzyl-L-glutamate) and copoly-(1 : 1)-(L-proline, γ-benzyl-L-glutamate) was observed. The NMR spectra of copoly-(1 : 3)-(L-proline, γ-benzyl-L-glutamate) showed no time dependence which can be ascribed to the conformational change in tetradeuteroacetic acid and the mixed solvent. From these experimental facts we concluded that copoly(3 : 1)-(L-proline, γ-benzyl-L-glutamate) and copoly-(1 : 1)-(L-proline, γ-benzyl-L-glutamate) can assume a poly-L-proline-like helical structure, while copoly-(1 : 3)-(L-proline, γ-benzyl-L-glutamate) can not. Moreover, the ratios of the γ-benzyl-L-glutamate residues which were incorporated into the stable poly-L-proline-II-like helical structure was estimated in copoly-(3 : 1)-(L-proline, γ-benzyl-L-glutamate) and copoly-(1 : 1)-(L-proline, γ-benzyl-L-glutamate).
  • Kazuo Tajima
    1970 Volume 43 Issue 10 Pages 3063-3066
    Published: 1970
    Released: March 27, 2006
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    The adsorbed amount and the surface tension at the air-solution interface of the solution of tritiated sodium dodecylsulfate in the presence of excess common inorganic salt have been accurately measured at 25°C. The radioactivity of tritium β-rays over the solution was counted with a sheet scintillation counter and the surface tension of the solution was measured by a drop volume method. In the sodium dodecylsulfate solution containing sodium chloride of 0.115 mol/l, the adsorbed amount of dodecylsulfate ions was saturated to give 4.33×10−10 mol/cm2 when the bulk concentration was higher than 5.0×10−4 mol/1000 g solution. In the presence of the excess inorganic salt common to the ionic surfactant in solution the Gibbs adsorption isotherm has been experimentally proved to be valid for n=1. Moreover, it was confirmed that the equation of state for the ionic adsorbed film on the salt-free solution proposed previously is also applicable to the ionic surfactant solution with the excess salt.
  • Jun-ichi Aihara, Motoyuki Tsuda, Hiroo Inokuchi
    1970 Volume 43 Issue 10 Pages 3067-3069
    Published: 1970
    Released: March 27, 2006
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    The absorption spectra of the gaseous olefin-TCNE complexes were successfully observed for the first time: the absorption maximum of the butene-TCNE complex was found at 28700 cm−1. The CT band of the methyl derivatives was shifted to a higher-energy region because of their steric effect. The systematic collection of the gaseous data made it possible to estimate the magnitude of the steric effect.
  • Yoshiko Kobayashi, Yoichi Iitaka, Yasumasa Kido
    1970 Volume 43 Issue 10 Pages 3070-3078
    Published: 1970
    Released: March 27, 2006
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    The crystal structure of the complex of 2-mercuri-4-methylphenol and 2-nitroso-4-methylphenol obtained in the modified Millon reaction was determined using three-dimensional X-ray diffraction data. The complex crystallizes in triclinic system, space group P\bar1, with a unit cell of dimensions a=10.26 Å, b=22.71 Å, c=5.61 Å, α=97.2°, β=93.1°, γ=91.1°, containing four complex molecules. Each of the two crystallographycally independent complex molecules both having essentially the same structure, forms a dimer with its nearest neighbor related by a center of symmetry through a pair of hydrogen bonds. The mercury atoms adopt a planar four-fold coordination with nitrogen, carbon and two oxygen atoms.
  • Haruhiko Tanaka, Hisao Negita
    1970 Volume 43 Issue 10 Pages 3079-3082
    Published: 1970
    Released: March 27, 2006
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    Bennema’s theory of crystal growth from a solution was modified and used in explaining fractionations of tritiated water in the crystal-growth processes of several inorganic hydrated salts from concentrated aqueous solutions. It was suggested that some water molecules in the aqueous solutions were free to become growth units which are not necessarily activated for entering the crystal surface. The dilution of tritiated water in the crystal was observed; this was explained in a satisfactory way in terms of the surface-diffusion model originally proposed by Burton, Cabrera, and Frank. On the contrary, the volume diffusion model was inadequate for interpreting the fractionation of tritium.
  • Keizo Suzuki, Masao Tsuchiya, Hideki Kadono
    1970 Volume 43 Issue 10 Pages 3083-3086
    Published: 1970
    Released: March 27, 2006
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    Diketopiperazine (DKP) was used as a model compound to investigate hydrogen bond interactions between the peptide bond and water under high pressure. The solubility of DKP in water was measured as a function of pressure up to about 6000 atm at 15,25 and 35°C. It was observed that the solubility decreases with increasing pressure up to about 4500 atm, and then increases above this pressure. The solubility follows a simple exponential dependence upon pressure at least below 4500 atm. The volume change ΔV accompanying the dissolution of DKP in water is obtained from this pressure dependence of the solubility. The values of ΔV are 5.2 and 5.9 ml/mol at 25° and 35°C, respectively. These values coincide well with those obtained from dilatometric measurements at 1 atm. The reason why the solubility is inverted at the pressure above and below 4500 atm is ascribed to the change of water structure brought about by the compression. The effect of pressure on proteins reported in the previous paper is discussed in relation to the present solubility results.
  • Tsuguo Yamaoka
    1970 Volume 43 Issue 10 Pages 3086-3090
    Published: 1970
    Released: March 27, 2006
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    In order to study the electronic spectra and stabilities of the ring protonated aromatic amines, π-electron structure of nineteen amino-substituted pentadienyl cations were calculated by the composite molecule method. The lower electronic transitions of these ions are assigned to the charge transfer from amino groups to the pentadienyl cation. Stability of the ground state depends on the extent of intramolecular charge transfer, which is determined by the position and number of amino-substitution. The amino group on 1-, 3- or 5-carbon atom greatly stabilizes the ground state while contribution of the amino group on the other position is quite small. Occurrence of the ring or amino protonation for various amino-substituted benzenes is shown to be well predicted by the calculated stabilization energy.
  • Toyoaki Kimura, Kenji Fueki, Zen-ichiro Kuri
    1970 Volume 43 Issue 10 Pages 3090-3095
    Published: 1970
    Released: March 27, 2006
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    Yields of scavenged electrons have been measured in MCH, 3MP, cumene and tert-butylbenzene at 20°C and −196°C. It has been found that the yield of scavenged electrons is considerably lower at −196°C in the glassy state than at 20°C in the liquid state. The temperature effect on electron scavenging indicates that the difference in the yields of scavenged electrons between the liquid and glassy states is attributed to the variation not of temperature but of the physical conditions of the matrix. We have also investigated the effect of composition in MCH-MTHF mixtures and that of the viscosity of the matrix upon the yield of scavenged electrons at −196°C, which has led us to the assumption that the extent of interactions between thermalized electrons and the matrix would affect the yield of scavenged electrons at −196°C. Since such interactions may be related to the mean free path of electrons, we have calculated the contribution of the electron jump distance to the electron scavenging efficiency. The calculated results appear to explain qualitatively the experimental results.
  • Shuichi Hamada, Yoshihiro Nakazawa, Toshiaki Shirai
    1970 Volume 43 Issue 10 Pages 3096-3101
    Published: 1970
    Released: March 27, 2006
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    The freezing behavior of supercooled liquid sulfur droplets were studied by means of a microscopic method. The number fraction of the solidified droplets in the experiments of continuous cooling on well-purified sulfur was only about 15% over the temperature range from 120°C to −70°C at the cooling rate of 0.20°C/min, and no abruptly discontinuous nucleation was found in these supercooling temperatures. The number fractions of the solidified droplets were found to be related to their volumes below −20°C. The nucleations in the well-purified liquid surfur droplets were confirmed to be a homogeneous process under these conditions. The specific nucleation rates per unit of volume were estimated to be 0.450, 1.13, and 1.16 cm−3sec−1 at the specified temperatures of −20, −40, and −50°C respectively. The dependences of (lnI+ΔFAkT) on 1⁄(ΔT)2T obeyed the theory of Turnbull and Fisher. The interfacial free energy of sulfur at the liquid-crystal surface was estimated to be 12.1 erg/cm2; this value was considered to be an appropriate one according to the Zadumkin consideration.
  • Hiroshi Yasuba, Tatsuro Imai, Kenichi Okamoto, Shigekazu Kusabayashi, ...
    1970 Volume 43 Issue 10 Pages 3101-3106
    Published: 1970
    Released: March 27, 2006
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    New organic charge transfer salts composed of an organic cation (pyrylium or thiopyrylium) and an organic anion (1,1,3,3-tetracyanopropenide or tricyanomethanide) were prepared. The absorption spectra were studied both in solution and in a solid. These salts have the charge transfer band in the visible region as a result of the electronic transition from the anion to the cation. The charge transfer bands of these salts in solution are sensitive to the nature of the solvent. The charge transfer band is observed in solvents with a low polarity; this band shifts toward a shorter wavelength in solvents with a high polarity. The increase in the polarity of the solvent causes a decrease in the apparent molar extinction coefficient. The charge transfer band in the solid shifts toward a shorter wavelength compared with that in the solution. In a single crystal, the polarized absorption spectrum shows a remarkable dichroism.
  • Shigehiro Konaka
    1970 Volume 43 Issue 10 Pages 3107-3115
    Published: 1970
    Released: March 27, 2006
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    The general quadratic potential constants of AsCl3 have been determined by the use of a combination of the mean amplitudes observed by gas electron diffraction and the vibrational frequencies. Those of AsF3 have been determined from the mean amplitudes, the centrifugal distortion constants given by microwave spectroscopy and the Coriolis coupling constants and the vibrational frequencies given by infrared spectroscopy on the basis of the molecular structure newly-determined by electron diffraction. By using these potential constants, zero-point average structures have been derived from the rg structures obtained by electron diffraction. The results have been found to be consistent with the average rotational constants, Bz, derived from the effective rotational constants, B0, observed by microwave spectroscopy according to the theory of vibration-rotation interactions. The final results, obtained by the use of a combination of the electron diffraction and microwave data, are:
    & r_z(As-Cl)=2.1621±0.0009 Å, θ_z(ClAsCl)=98°38’±22’
    & r_z(As-F)=1.7080±0.0004 Å, and θ_z(FAsF)=95°58’±17’.
    Formulas for calculating the sum of perpendicular mean amplitudes for pyramidal XY3-type molecules have been derived and used to reduce rg to rz.
  • Akinori Hasegawa, Yasuyoshi Michihara, Masaji Miura
    1970 Volume 43 Issue 10 Pages 3116-3121
    Published: 1970
    Released: March 27, 2006
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    The ESR spectrum of the Mn2+ ion in an aqueous solution of a surfactant is affected by its concentration. Sodium dodecyl sulfate and sodium decyl sulfate were employed as surfactants in this study. The linewidth of the Mn2+ ion is independent of the concentration of the surfactant in the low-concentration range, but it increases over a certain concentration range and then becomes constant. Two values of CMC were observed by measurements of the conductivity corresponding to the concentrations, where the linewidth of Mn2+ changed abruptly with the concentration of the surfactant. The linewidth broadening above the first CMC was interpreted as being due to the formation of an outer-sphere complex of the Mn2+ ion with a surfactant micelle. The interaction between the counterion and micelle was also investigated on the basis of the ESR spectra of the Mn2+ ion with regard to the effects of the kind of surfactant, the temperature, foreign electrolytes, etc.
  • Yukio Kubota
    1970 Volume 43 Issue 10 Pages 3121-3125
    Published: 1970
    Released: March 27, 2006
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    When DNA-acridine dye complexes were excited by a visible light which was not absorbed by DNA, phosphorescence and a delayed fluorescence of the dye were observed. It was found, by comparing the excitation spectra with the absorption spectra, that the monomeric dyes mainly contribute to the fluorescence and phosphorescence emissions. The delayed fluorescence was interpreted as a result of the triplet-triplet annihilation which arises from two triplet dye molecules placed very close together. The decrease in the delayed fluorescence on the denaturation of DNA indicates that the interaction between the two triplets is sensitive to the conformation of the macromolecule.
  • Yukio Kubota
    1970 Volume 43 Issue 10 Pages 3126-3130
    Published: 1970
    Released: March 27, 2006
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    When frozen aqueous solutions of DNA-acridine dye complexes or nucleotide-dye mixtures were excited by ultraviolet light, a sensitized delayed fluorescence of the dye was observed. This delayed fluorescence was interpreted by means of a mechanism in which the excitation energy is transferred from the triplet state of the nucleotides to the first excited singlet state of the dye. The efficiency and decays of the sensitized delayed fluorescence revealed that the energy transfer depends greatly on the separation between the energy donor and acceptor and that donor-acceptor pairs spaced very closely are important in the energy transfer. In DNA-acridine dye complexes, the thymine triplet seems to play the most important role as an energy donor. The decrease in the delayed fluorescence on the denaturation of DNA indicates that the energy transfer is sensitive to the conformation of the macromolecule.
  • Hideyuki Ishida, Hiroshi Takahashi, Hiroshi Tsubomura
    1970 Volume 43 Issue 10 Pages 3130-3136
    Published: 1970
    Released: March 27, 2006
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    Quenching of phosphorescence and fluorescence of aromatic hydrocarbons adsorbed on powdered porous glass or silica gel have been examined as a function of oxygen pressure. It has been found that the phosphorescence quenching at low temperature can be explained mostly by assuming that only those aromatic molecules having an oxygen molecule or molecules within an effective interaction radius are nonphosphorescent (static quenching model). The fluorescence quenching occurs only at much higher oxygen pressures and it has been proposed that contact pairs between aromatic and oxygen molecules, which have shorter intermolecular distances compared to the distances effective for the phosphorescence quenching and give rise to the charge-transfer absorption bands, are relevant. It has been observed that the excimer fluorescence of naphthalene appearing at a higher sample concentration is more strongly affected by oxygen than the monomer fluorescence. The emission spectra from naphthalene-porous glass adsorbate immersed in liquid oxygen and nitrogen have also been examined. The formation of the singlet oxygen (1Δg or 1Σg+) through the interaction of oxygen with triplet molecules has been confirmed by use of the peroxidation reaction of adsorbed anthracene.
  • Miyoshi Uehara, Jun-ichi Nakaya
    1970 Volume 43 Issue 10 Pages 3136-3142
    Published: 1970
    Released: March 27, 2006
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    The effects of intramolecular hydrogen bonding on the polarographic reduction potentials (E1⁄2) of several azomethines, such as N-salicylidenemethylamine, N,N′-bis(salicylidene)ethylenediamine, N-salicylideneaniline, N-salicylidene-o-aminophenol, and N-benzylidene-o-amino-p-substituted phenols, have been studied in aqueous and non-aqueous solutions. Contrary to expectations, a larger negative shift of E1⁄2 was observed in the case of o-OH-substituted azomethines than in that of unsubstituted azomethines in buffer solutions. On the other hand, the E1⁄2 of the substituted compounds shifted 0.3–0.4V toward the positive side in dimethylformamide or acetonitrile. The relative strengths of hydrogen bonds, as estimated from the positive shifts of E1⁄2, were 6–10 kcal/mol. It has been proposed, from the hydrogen bond strength, the UV spectra, and the p-substituent effects, that the introduction of an o-OH group into the phenylimino ring provides not a periperpendicular conformation, but a coplanar configuration, by means of the formation of the O–H···N hydrogen bond.
  • Seiichiro Koda, Akira Misono, Yasuzo Uchida
    1970 Volume 43 Issue 10 Pages 3143-3149
    Published: 1970
    Released: March 27, 2006
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    Several mononuclear cobalt oxygen complexes in solutions have been investigated by means of ESR measurements. When a pyridine (and also substituted pyridines, N,N-dimethylformamide, dimethyl sulfoxide, and hexamethylphosphoramide) solution of a bis-salicylaldehyde-imine cobalt-(II) complex (N,N′-ethylene-bis(salicylideneiminato)cobalt(II), and N,N′-ethylene-bis(3-methoxysalicylideneiminato)cobalt(II)) was exposed to oxygen, there appeared a reversible ESR signal, in which a hf structure of eight lines caused by a mononuclear cobalt was observed. This spectrum could be analysed by considering the species to be essentially a superoxide cobalt(III). We tried to explain the deviations in the ACo and the g values of the species from solvent to solvent by considering that the solvent coodinates to the cobalt complex in the trans position against the coodinated oxygen. As a comparative study, the mononuclear oxygen adduct of di(salicylal)-3,3′-diimino-di-n-propylamine-cobalt(II) was also studied in the above solvents.
  • Masayoshi Nakahara, Akio Urushiyama, Yasuo Satoh, Yukio Kondo
    1970 Volume 43 Issue 10 Pages 3150-3155
    Published: 1970
    Released: March 27, 2006
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    The mono-, di- and tricholatocobalt(III) and chromium(III) complexes and cobalt complex cholates, including the following new compounds, have been prepared: [Co chol (NH3)5] X2 (X=chol, Cl), [M chol2 en2]Cl (M=Co, Cr), [Co chol3 (NH3)3] and [Co en3]chol3. The absorption spectra of these complexes in the visible, ultraviolet, and infrared regions have been measured and compared with those of the corresponding acetato- or acido-complexes.
  • Hidetake Kakihana, Toshihiko Amaya, Masunobu Maeda
    1970 Volume 43 Issue 10 Pages 3155-3158
    Published: 1970
    Released: March 27, 2006
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    The hydrolysis equilibria of the copper(II) ion in heavy water have been studied at 25°C by measuring the deuterium-ion concentration by means of a commercial glass electrode. The total copper(II) concentration was varied between 50 and 90 mM, while the concentration of the perchlorate ion was held constant at 3M by the addition of NaClO4. A hydrolyzed copper(II) perchlorate solution was gradually acidified up to the point where hydrolysis was negligible by the use of constant-current coulometry. The experimental data, which indicate a slight hydrolysis in the log d range from –4.0 to –5.26, can be explained by assuming these equilibria;
    & Cu^2++D_2O=CuOD^++D^+,logβ_1,1=-7.71±0.07;
    & 2Cu^2++2D_2O=Cu_2(OD)_2^2++2D^+,logβ_2,2=-11.46±0.04.
  • Kazuyoshi Takahashi, Minoru Yoshida, Takejiro Ozawa, Iwaji Iwasaki
    1970 Volume 43 Issue 10 Pages 3159-3164
    Published: 1970
    Released: March 27, 2006
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    The catalytic action of bromide on the oxidation of to iodine iodate by potassium permanganate in sulfuric acid solution has been utilized for the microdetermination of bromine in silicate rocks. The method described consists of decomposing the silicate-rock sample by fusion with potassium hydroxide, leaching the melt with water, oxidizing bromide to bromine with potassium permanganate, extracting by benzene, and finally determining the bromine by the catalytic method. By this method, the bromine in samples with more than 0.04 ppm can be determined rapidly and accurately, using only 0.25–0.5 g of samples.
  • Masahiro Tsubouchi
    1970 Volume 43 Issue 10 Pages 3164-3166
    Published: 1970
    Released: March 27, 2006
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    A spectrophotometric method is proposed for the determination of diphenhydramine in pharmaceutical preparations. The method is based on an addition-compound formation between diphenhydramine and the tetrabromophenolphthalein ethyl ester in 1,2-dichloroethane. Beer’s law is obeyed over the range of 2.0×10−6–1.0×10−5M of diphenhydramine at 594 mμ. Optimum conditions are described. The effect of diverse substances and the composition of the colored species were also investigated.
  • Tairoku Yano, Hiroshi Kobayashi, Keihei Ueno
    1970 Volume 43 Issue 10 Pages 3167-3170
    Published: 1970
    Released: March 27, 2006
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    trans,2,3-Dinitrilo-1,2,3,4-tetrahydronaphthalene-N,N,N′,N′-tetraacetic acid was synthesized by the carboxymethylation of trans-2,3-diaminotetrahydronaphthalene. The acid dissociation constants as well as the chelate stability constants for alkaline earth metal ions were determined by a potentiometric method. The results were compared with the values of other complexane ligands of the cycloalkane family.
  • Takayoshi Sakai
    1970 Volume 43 Issue 10 Pages 3171-3175
    Published: 1970
    Released: March 27, 2006
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    Indoferron is shown to be a useful spectrophotometric reagent for the determination of zirconium(IV) and iron(III). An excess reagent reacts with zirconium(IV) and iron(III) to form blue complexes, which have absorption maxima at 605 and 590 mμ respectively against the reagent blank. The maximum absorbances of the solutions containing the complexes are obtained in the pH range from 3.6 to 3.7 for zirconium(IV), and in that from 3.9 to 4.1 for iron(III). The former complex is stable for 1 hr, and the latter, for 4 hrs. The color systems obey Beer’s law in 25 ml over the ranges up to 40 μg Zr and up to 50 μg Fe respectively. The molar absorptivities of the complexes are calculated to be 3.18 ×104 for zirconium(IV) and 1.81 ×104 for iron(III). The sensitivities of the reactions are 0.0038 μg Zr/cm2 and 0.0039 μg Fe/cm2 for an absorbance of 0.001. As for composition, the complexes used have a metal-to-ligand ratio of 1:3 for zirconium-(IV) and 1:2 for iron(III). The apparent formation constant of the complex for iron(III) is calculated to be 7.81 ×1010.
  • Takeshi Nakai, Yoshio Ueno, Makoto Okawara
    1970 Volume 43 Issue 10 Pages 3175-3181
    Published: 1970
    Released: March 27, 2006
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    The following ring analogs of 2-dimethylamino-1,3-dithiolanylium perchlorate (Ia) were prepared: 2-dimethylamino-1,3-dithianylium perchlorate (IV), 2-dimethylamino-1,3-dithiepanylium perchlorate (V) and an open-chain analog, bis(methylthio)dimethylaminocarbonium perchlorate (VI). In order to investigate the structural effect on the reactivities of the tri(hetero)carbonium ions at two reactive sites, i. e., the centered carbon (sp2) (a) and the S-methylene carbon (sp3) atoms (b), the reactions of these carbonium ions with hydroxide ion (mode A) and with N,N-dimethyldithiocarbamate ion (mode B), respectively, were studied at 30°C. The rates of mode A of these carbonium ions, relative to that of Ia, are 1 : 15.0 (IV) : 32.5 (V) : 1.06×104 (VI), and of mode B are 1 : 6.5 : 23.5 : ≈2.0×104. In their electronic spectra a definite trend that as the ring-size increases there is a strong shift of absorption maxima toward the lower energies was observed. The fact suggests that the stability of the carbonium ion decreases with an increase in ring-size. On the basis of the schematic energy profiles for the two modes as well as the structural and kinetical aspects, it has been assumed that one of common factors contributing to the ringsize effect on both reactivities would be the stability of the carbonium ion.
  • Katsuyuki Ogura, Teruo Matsuura
    1970 Volume 43 Issue 10 Pages 3181-3187
    Published: 1970
    Released: March 27, 2006
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    Irradiation of 2,4,6-tri-t-butyl-4-bromo-2,5-cyclohexadienone (X) in various solvents yielded 2,4,6-tri-t-butylphenol (XIII) in high yields. It was shown that 2,4,6-tri-t-butylphenoxy radical (XII) was formed as an intermediate and that the light of shorter wavelengths than 450 mμ accelerated the hydrogen abstraction of XII. The rate of the photochemical decomposition of X decreased in the order: n-hexane, N,N-dimethylformamide and acetic acid. This and the sensitized reaction suggest that the formation of XII from X may result from the n* triplet state of X. On the other hand, irradiation of 2,4,6-tri-t-butyl-4-nitro-2,5-cyclohexadienone (XI) afforded 2,6-di-t-butyl-p-quinone (XV) and 2,4,6-tri-t-butylphenol (XIII), indicating a homolytic cleavage of the C–NO2 bond.
  • Katsuyuki Ogura, Teruo Matsuura
    1970 Volume 43 Issue 10 Pages 3187-3194
    Published: 1970
    Released: March 27, 2006
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    Irradiation of 2,4-di-t-butyl-4,5-dihydroxy-2,5-cyclohexadienone (V) in methanol afforded a β-diketone (VIII) in a 68% yield. Diketone VIII was also formed on photolysis of a suspension of V in petroleum ether (62%) and an aqueous alkaline solution of V (56%). Photolysis of 2,4-di-t-butyl-4-hydroxy-5-methoxy-2,5-cyclohexadienone (VI) in various solvents yields IXa as a main product. On irradiation of VI in methanol, XI which might be formed by the addition of methanol to IXb was also isolated. Irradiation of 2,4,6-tri-t-butyl-3-methoxy-4-hydroxy-2,5-cyclohexadienone (VII) in a variety of solvents gave a cyclopentadienone (XIII) in high yields. It is reasonable to assume that the cyclopentadienone XIII is formed by elimination of methanol from a 2-cyclopentenone derivative (XII). The formation of XIII from VII was sensitized by benzophenone and acetophenone, and quenched by piperylene. The mechanisms of these reactions are discussed.
  • Koichi Hatada, Kazuhiko Nagata, Heimei Yuki
    1970 Volume 43 Issue 10 Pages 3195-3198
    Published: 1970
    Released: March 27, 2006
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    The 13C NMR spectra of alkyl vinyl ethers were investigated at 22.5°C with neat liquid at 15.09 MHz. When the alkyl group of the ether becomes more electron-donating, the chemical shift of the α-carbon of the vinyl group shifts to a higher field, and that of the β-carbon, to a lower field. From these results, it was concluded that the contribution of the resonance form, \barCH2–CH=\overset+O–R, in the ether decreases in the order of the increasing electron-repelling power of the alkyl group. Good correlations were obtained between the chemical shifts of the vinyl group and the reactivity of vinyl ether in the cationic reaction. When the ether becomes more reactive, the chemical shift of the α-carbon shifts to a higher field, and that of the β-carbon to a lower field. This fact clearly shows that the attack of the proton on the β-carbon is not the rate determining step in the cationic reaction of the vinyl group. Linear relations were obtained between the chemical shifts of β-methylene protons and of β-carbon, but no correlation was obtained between the chemical shifts of the α-methine proton and of the α-carbon.
  • Toshiki Otake
    1970 Volume 43 Issue 10 Pages 3199-3205
    Published: 1970
    Released: March 27, 2006
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    Two isomeric mono-O-tritylsucroses were isolated from a mixture of tritylated sucrose which had been obtained by the reaction of sucrose and trityl chloride in the ratio of 1 : 1.2 by mole. The structures of these two isomers were established by the application of gas chromatography and NMR spectroscopy to appropriate derivatives. One of the two substances is 6′-mono-O-tritylsucrose, and the other is 6-mono-O-tritylsucrose, which is crystallized as white needles. The detritylation of mono-O-trityl-O-acetylsucroses yielded hepta-O-acetylsucroses, which were confirmed by a study of their NMR spectra to be 2,3,4,6,1′,3′,4′- and 2,3,4,1′,3′,4′,6′-hepta-O-acetylsucrose. No migration of the acetyl group on the sucrose molecule was observed during the detritylation procedure.
  • Noboru Sugiyama, Yoshiaki Sato, Choji Kashima
    1970 Volume 43 Issue 10 Pages 3205-3209
    Published: 1970
    Released: March 27, 2006
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    The irradiation of 2,6-diphenyl-4H-thiopyran-4-one (1) or 2,6-diphenyl-4H-pyran-4-one (2) in an alcohol in the presence of oxygen gave benzoic acid and a benzoylacetic acid ester, while that of 2 in benzene or 2,6-dimethyl-4H-thiopyran-4-one (5) in various solvents gave the corresponding cage dimer, (9) or (10). No photoreaction could be observed in case of the irradiation of 1,2,6-trimethyl-4-pyridone (3) and 6-methyl-1,2-diphenyl-4-pyridone (4). A reaction mechanism via the triplet state of the substrate was also proposed.
  • Eizo Matsumura, Masahiro Ariga, Takahiko Ohfuji
    1970 Volume 43 Issue 10 Pages 3210-3214
    Published: 1970
    Released: March 27, 2006
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    The Reissert-Kaufmann-type reaction of substituted N-methoxy-4-nitropyridinium methylsulfates gave the corresponding 2-cyano-4-nitropyridines in satisfactory yields. When 3-methyl-4-nitropyridine N-oxide was used as the starting material, a cyano group was introduced not into the 6-position, but into the 2-position. This preference may be explained by proposing a hyperconjugation effect of the 3-methyl group. The resulting nitriles were quantitatively hydrolyzed to the corresponding 4-nitropicolinic acids. These reactions provided a new route for the preparation of nitropyridinecarboxylic acids from pyridine homologues. Further, some nucleophilic substitution reactions of the products were carried out.
  • Yoshiaki Araki, Aritsune Kaji
    1970 Volume 43 Issue 10 Pages 3214-3219
    Published: 1970
    Released: March 27, 2006
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    Various aryl thionobenzoates were prepared. When maintained at elevated temperatures, they rearranged smoothly to aryl thiolbenzoates. The mechanism of this rearrangement was kinetically investigated. The rearrangement rates were correlated with the first-order kinetic equation, and the rearrangement was found to be facilitated by substitution with an electron-withdrawing group in the migrating aromatic rings. The Hammett ρ value was found to be 2.11 in diphenyl ether at 200.5°C. The entropies of activation were negative. A linear free-energy relationship existed between this rearrangement and the rearrangement of O,S-diaryl dithiocarbonates. From these observations, a four-membered cyclic structure can be suggested as the transition state for this rearrangement. The present results indicate that the existence of hetero atoms directly bound to the thiocarbonyl group is not essential for the thermal rearrangement with intramolecular 1,3 aryl migration from oxygen to sulfur.
  • Chung-gi Shin, Mitsuo Masaki, Masaki Ohta
    1970 Volume 43 Issue 10 Pages 3219-3223
    Published: 1970
    Released: March 27, 2006
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    Synthetic studies of α,β-unsaturated α-nitrocarboxylic esters and the corresponding α-amino compounds are described. When α,β-unsaturated carboxylic ester was treated with fuming nitric acid, two products, α,β-unsaturated α-nitrocarboxylic ester and α-hydroxy-β-nitrocarboxylic ester, were formed. The former was converted into β-methoxy-α-nitrocarboxylic ester by treatment with methanol in the presence of a base such as sodium methoxide or sodium acetate. Reduction of β-methoxy-α-nitrocarboxylic esters with aluminum amalgam and the subsequent distillation of the products afforded α,β-unsaturated α-aminocarboxylic esters and α-hydroxyamino-β-methoxycarboxylic esters, which were confirmed by their N-phthaloylglycyl derivatives.
  • Saburo Inokawa, Yoshimi Tsuchiya, Hiroshi Yoshida, Tsuyoshi Ogata
    1970 Volume 43 Issue 10 Pages 3224-3226
    Published: 1970
    Released: March 27, 2006
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    3,5-O-Benzylidene-6-deoxy-6-diethoxyphosphinyl-1,2-O-isopropylidene-α-D-glucofuranose was prepared in an 80% yield by heating a solution of 3,5-O-benzylidene-6-deoxy-6-iodo-1,2-O-isopropylidene-α-D-glucofuranose (1) in an excess of triethyl phosphite (5). Similarly, 6-deoxy-6-diethoxyphosphinyl-1,2;3,4-di-O-isopropylidene-α-D-galactopyranose was prepared in a 95% yield from 6-deoxy-1,2;3,4-di-O-isopropylidene-α-D-galactopyranose (2), and (5); 5-deoxy-5-ethoxyphenylphosphinyl-1,2-O-isopropylidene-3-O-methyl-α-D-xylofuranose was prepared in a 90% yield from 5-bromo-5-deoxy-l,2-O-isopropylidenne-3-O-methyl-α-D-xylofuranose and diethyl phenylphosphonite; 3,5-O-benzylidene-6-deoxy- 1,2-O-isopropylidene-6- (N,N′-tetraethyldiaminophosphinyl)-α-D-glucofuranose was prepared in a 44% yield from 1 and ethyl N,N′-tetraethylphosphorodiamidite (7); 6-deoxy-1,2; 3,4-di-O-isopropylidene-6-(N,N′-tetraethyldiaminophosphinyl)-α-D-galactose was prepared in a 70% yield from 2 and 7.
  • Nobuo Mori, Yoshihiro Asabe, Junko Tatsumi, Yojiro Tsuzuki
    1970 Volume 43 Issue 10 Pages 3227-3231
    Published: 1970
    Released: March 27, 2006
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    The νNH values of monomeric alkylmethylamines in carbon tetrachloride solutions are associated with the rotational isomerism about the N–C bond. In the series of N-alkylaminoalkano-nitriles, the intramolecular hydrogen-bonding interaction of the NH group with the π-electrons of the CN group was deduced on the basis of the νNH values and a model examination; in the α-series, the NH group probably interacts exclusively, and in the β-series it partially interacts, but in the γ-series it shows no interaction.
  • Jugo Koketsu, Seiji Kojima, Yoshio Ishii
    1970 Volume 43 Issue 10 Pages 3232-3236
    Published: 1970
    Released: March 27, 2006
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    The reactions between dialkyl dimethylphosphoramidite, Me2NP(OR)2, and β-propiolactone were carried out in various solvents at 80°C. Two kinds of reaction products were separated on a silica gel by elution with benzene-ethanol (4:1 v/v). The first species eluted was N,N-dimethyl-O-alkyl 2-alkoxycarbonylethylphosphoramidate, (RO)P(O)(NMe2)CH2CH2CO2R. The fraction having lower Rf value contained dialkyl 2-N,N-dimethylcarbamoylethylphosphonate, (RO)2P(O)CH2CH2CONMe2. The reaction mechanism is discussed from kinetic study.
  • Hidehiro Higashi, Kazu Kurosawa, Hisashi Matsumura
    1970 Volume 43 Issue 10 Pages 3236-3238
    Published: 1970
    Released: March 27, 2006
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    5-Styryl-, 5-(p-bromostyryl)-, 5-(p-chlorostyryl)-, 5-(p-methoxystyryl)-, 5-(p-methylstyryl)-, 5-(m-chlorostyryl)- and 5-(m-methylstyryl)tropolone were synthesized by the Wittig reaction of 5-formyltropolone. Their UV and NMR spectra were determined.
  • Shinsaku Fujita, Tamejiro Hiyama, Hitosi Nozaki
    1970 Volume 43 Issue 10 Pages 3239-3241
    Published: 1970
    Released: March 27, 2006
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    The acid-catalyzed ring-opening of 9-ethoxycarbonyl-9-aza-bicyclo[6.1.0]nonane (1) and-4-nonene (2) is reported to give normal products 3a and 11a, respectively, together with several transannular products.
  • Takeshi Irimajiri, Hiroshi Yoshida, Tsuyoshi Ogata, Saburo Inokawa
    1970 Volume 43 Issue 10 Pages 3242-3245
    Published: 1970
    Released: March 27, 2006
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    The syntheses of some derivatives of D-glucuronic acid from D-glucofuranurono-6→3-lactone have been investigated. That is, 5-bromo-5-deoxy-1,2-O-isopropylidene-β-L-idofuranurono-6→3-lactone (2) and 5-bromo-5-deoxy-1,2-O-isopropylidene-α-D-glucofuranurono-6→3-lactone (3) were prepared by heating 1,2-O-isopropylidene-5-O-(p-toluenesulfonyl)-α-D-glucofuranurono-6→3-lactone (1) with lithium bromide in dimethylformamide (DMF); methyl 5-O-(p-toluenesulfonyl)-β-D-glucofuranurono-6→3-lactone, 5-bromo-5-deoxy-α-L-idofuranurono-6→3-lactone, and 5-bromo-5-deoxy-β-D-glucofuranurono-6→3-lactone were prepared by heating 1, 2, and 3 respectively in methanol in the presence of strong acidic ion-exchange resins; 5-deoxy-1,2-O-isopropylidene-α-D-glucofuranurono-6→3-lactone (7) was prepared by the reaction of 2 with thiolacetic acid of benzylmercaptan in pyridine or by the reaction of 2 with triethyl phosphite; 5-bromo-5-deoxy-1,2-O-isopropylidene-β-L-ido-hexodialdo-3,6-furanoid(6S)-1,4-furanose (8) was prepared by the reduction of 2 with lithium aluminum hydride; 1,2-O-isopropylidene-5-O-(p-toluenesulfonyl)-α-D-gluco-hexodialdo-3,6-furanoid-1,4-furanose and 1,2-O-isopropylidene-5-O-(p-toluenesulfonyl)-α-D-glucofuranose (10) were prepared by the reduction of 1 with lithium aluminum hydride, and 1,2;3,6-di-O-isopropylidene-5-O-(p-toluenesulfonyl)-α-D-glucofuranose and 3,6-di-O-acetyl-1,2-O-isopropylidene-5-O-(p-toluenesulfonyl)-α-D-glucofuranose were prepared by the acetonation and the acetylation of 10 respectively.
  • Michio Iwai, Kiichiro Nakajima, Akio Uno, Satoe Hase, Ikuko Takeuchi, ...
    1970 Volume 43 Issue 10 Pages 3246-3251
    Published: 1970
    Released: March 27, 2006
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    Modified gramicidin S pep tides, cyclo(Ser-Orn-Ser-D-Phe-Pro)2 and cyclo(Ser-Orn-Ser-D-Phe-Pro), were synthesized in order to clarify the correlation between the component amino acids and the antibiotic activity. To obtain the cyclic peptides, we examined several sets of conditions for cyclization reactions. The antibiotic activity of these peptides could not be found against some microorganisms in vitro. It was concluded that the lipophilic amino acids residues are the essential groups contributing to gramicidin S activity.
  • Yasutsugu Shimonishi
    1970 Volume 43 Issue 10 Pages 3251-3255
    Published: 1970
    Released: March 27, 2006
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    Elongation reactions of the S-sulfonate of the A-chain of bovine insulin were carried out with acylamino acid-active esters or with acylpeptide azide; the following derivatives of the A-chain were thus synthesized: S-sulfonates of NG-nitro-L-arginyl-, L-lysyl-NG-nitro-L-arginyl-, and L-prolyl-L-prolyl-L-glutaminyl-Nε-benzyloxycarbonyl-L-lysyl-NG-nitro-L-arginyl-A-chain. Thus, this was demonstrated to be a useful procedure for the partial synthesis of proinsulin.
  • Tadashi Okuyama, Takayuki Fueno, Junji Furukawa
    1970 Volume 43 Issue 10 Pages 3256-3259
    Published: 1970
    Released: March 27, 2006
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    The acid-catalyzed hydrolysis of cis- and trans-styvyl ethyl ethers (SEE) and several of their ring-substituted derivatives has been kinetically investigated in 80% aqueous dioxane. It has been found that these ethers are less reactive than vinyl ethyl ether by a factor of ca. 500 and that all the cis isomers studied are about twice as reactive as the corresponding trans isomers. The hydrolysis of the substituted ethers at 35°C has proved to obey the Hammett relation with the reaction constants ρ=−1.07 and −0.70 for the cis and the trans isomers, respectively. All these results appear to be interpretable at least qualitatively in terms of the reaction scheme involving the rate-determining protonation to the β-carbon atom.
  • Akira Misono, Yasuzo Uchida, Kunikazu Yamada
    1970 Volume 43 Issue 10 Pages 3259-3262
    Published: 1970
    Released: March 27, 2006
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    Properties of vinyl chloride-ethylene copolymers rich in vinyl chloride have been studied by means of infrared as well as NMR spectroscopy and dynamic mechanical testing. The infrared and NMR spectra of the copolymer indicate that crystallinity decreases with decreasing sequence length of the vinyl chloride segment. The copolymer containing more than 80 mol % vinyl chloride shows optical melting point, a plot of which versus logarithmic composition satisfies Flory’s relationship. Temperature dispersion curve of elastic modulus E′ of the copolymer also indicates that the crystalline region of vinyl chloride segments disappears as the ethylene content increases. Glass transition temperature as determined by loss modulus E″ fits Gordon-Taylor’s relationship well provided the coefficient k equals unity.
  • Hisaya Oki, Eishin Kyuno, Ryokichi Tsuchiya
    1970 Volume 43 Issue 10 Pages 3263-3264
    Published: 1970
    Released: March 27, 2006
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  • Shunsuke Nakama, Kimiaki Imafuku, Hisashi Matsumura
    1970 Volume 43 Issue 10 Pages 3265-3267
    Published: 1970
    Released: March 27, 2006
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