Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 42 , Issue 1
Showing 1-50 articles out of 64 articles from the selected issue
  • Sukenari Tsunakawa
    1969 Volume 42 Issue 1 Pages 1-4
    Published: 1969
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    High resolution mass spectra of thymidine were studied by Mattauch-Herzog geometry mass spectrograph. The element map of it was presented and the fragmentation processes were shown by solid or dotted lines on the map. The spectra were measured with higher accelerating voltages (about 0.1%) in order to obtain many metastable peaks on the photographic plate. By a single focusing mass spectrometer ten metastable peaks were measured and “intentionally defocused” high resolution spectra gave twenty five diffused peaks with slight shifts to the high mass region though no metastable peaks were observed under normal operating conditions.
  • Kiyoshi Arakawa, Nobuo Takenaka
    1969 Volume 42 Issue 1 Pages 5-9
    Published: 1969
    Released: March 27, 2006
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    Ultrasonic investigations of the water-dioxane system were made by means of an ultrasonic pulse technique. The ultrasonic velocity and absorption of the solutions were measured in the frequency range from 5 to 45 Mc/sec. The temperature was varied from 20 to 60°C. It was observed in the velocity vs. concentration curves obtained at various temperatures that all curves converged at 0.03–0.04 mol fraction of dioxane. The ultrasonic absorption of pure dioxane was found to increase with the rise of temperature, which might be ascribed to the vibrational relaxation. From the ultrasonic absorption data obtained for the solutions of the water-dioxane system in various compositions and temperatures it was observed that at 0.3–0.4 mol fraction of dioxane an absorption peak was present in the absorption vs. concentration curve, and also that there was no shift of the concentration at the peak with the variation of temperature. Some discussion on the structure of the water-dioxane system was given from the ultrasonic data obtained.
  • Akira Kuboyama, Ryuichi Yamazaki, Sanae Yabe, Yoshio Uehara
    1969 Volume 42 Issue 1 Pages 10-15
    Published: 1969
    Released: March 27, 2006
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    The positions and intensities of the n→π* absorption bands in solutions at 77°K (in the rigid glass state) and at 201°K (in the liquid state) have been studied in comparison with those at room temperature. At 201°K the positions and intensities are similar to those at room temperature. At 77°K some distinct facts have been found in EP (ether-isopentane (1:1) mixture) which are different from those which hold in the liquid state: 1) In desoxybenzoin the absorption is remarkably weak in intensity. 2) In some α-diketones and β-naphthoquinone, the n→π* bands shift greatly to the blue. 3) In β-naphthoquinone the absorption is remarkably strong in intensity. Discussions of the obtained results have been presented.
  • Syozi Noda, Kenji Fueki, Zen-ichiro Kuri
    1969 Volume 42 Issue 1 Pages 16-19
    Published: 1969
    Released: March 27, 2006
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    The energy levels of solvated electrons have been calculated as a function of the static dielectric constant and of the cavity radius on the basis of a continuous dielectric model with an adiabatic approximation, and a contour diagram has been drawn up for the transition energy of solvated electrons. Using this diagram and the observed absorption spectra, the quantities on solvated electrons in alcohols have been estimated. The cavity radius, R, ranges from 0.9 to 1.6 Å, the charge distribution for the ground state, from 2.4 to 3.2 Å, and the variation in cavity radius, from 0.50 to 0.60 Å, at room temperature. From the calculations of the temperature dependence, d(hv)/dt, of the transition energy, it can be said that, for solvated electrons in alcohols, the contribution to d(hv)/dt of the change in R with the temperature is rather more dominant than the change in the static dielectric constant with the temperature. It has also been found that there exists a correlation between the dR/dt value and the ratio of the number of the OH bond to the total number of bonds involved in each alcohol.
  • Hiroshi Kumanomido
    1969 Volume 42 Issue 1 Pages 20-24
    Published: 1969
    Released: March 27, 2006
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    In order to elucidate the mechanism of the precipitation of humic acid by two cationic polyelectrolytes, the n-butylamine-epichlorohydKin condensation polymer (BECP) and the cyclohexylamine-epichlorohydrin condensation polymer (CECP), electrophoresis and conductometric titration were made in conjunction with precipitation experiments in various concentrations of humic acid with an optimum dosage of cationic polyelectrolyte. The results of these experiments indicated that a cationic polyelectrolyte precipitates the humic acid by combining stoichiometrically with the negatively-charged groups of the humic acid. A possible mechanism for the precipitation was proposed schematically on the basis of the experimental results obtained.
  • Masaharu Morita, Shunji Kato
    1969 Volume 42 Issue 1 Pages 25-35
    Published: 1969
    Released: March 27, 2006
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    Flash photolytic studies of the transient intermediates produced in the flash excitation of an aqueous buffered solution of the photosensitizing dye “thiopyronine” were undertaken in order to obtain direct insight into the reaction mechanism of the photosensitizing action of the dye. As had been expected from the structural similarity to a well-known photosensitizer, methylene blue, previously reported on, the flash excitation of thiopyronine, in a deaerated buffered solution at pH 7.4 without any substrate, produced three transient intermediates: a triplet-state (Dt), a half-oxidized form (Oxd), and a half-reduced form or semiquinone (Red) of the dye. Red and Oxd were generated simultaneously through electron tansfer reactions, i.e., Dt+Dt→Red+Oxd and Dt+D→Red+Oxd, where D is the dye in the ground state. Thiopyronine solutions containing some reducing and oxidizing agents were studied in order to identify the intermediates. The absorption spectra of these intermediates were identified, and their reaction mechanism studied. The rate constants of some elementary processes obtained are:
    Dtk1=2.36×103sec−1
    Dt+Dtk=7.69×108M−1sec−1
    Dt+D→k″=7.69×108M−1sec−1
    Red+Red→k6=(1–2)×109M−1sec−1
    Oxd→k7=(1–3)×103sec−1
    Dt+EDTA→k8=1.6×107M−1sec−1
    Dt+ATU→k9≈small
    Oxd+ATU→k10(2–5)×106M−1small
    The high efficieny of thiopyrinine in its Photodynamic effect was discussed in connection with the high quantum yield of triplet-state production and the high reversibility of the high reversibility of the photochemical redox reaction of the dye.
  • Takeshi Murakami, Sachio Murakami, Ryoichi Fujishiro
    1969 Volume 42 Issue 1 Pages 35-40
    Published: 1969
    Released: March 27, 2006
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    The heat of mixing was measured for binary mixtures of pyridine derivatives (α-picoline, β-picoline, γ-picoline, and 2,6-lutidine) with benzene or cyclohexane at 25.0±0.01°C, and for a binary mixture of pyridine with benzene, or cyclohexane, at 30.0±0.01°C. The small values of the heat of mixing for pyridine derivatives-a benzene system were interpreted as an indication of strong specific interactions between pyridine derivatives and benzene. By treating the results in the manner described in a previous paper (Bull. Chem. Soc. Japan, 39, 720 (1966)), the specific interaction energies of pyridine derivatives with benzene were estimated. The strengths of the molecular interaction energy were in the order: γ-picoline>pyridine>β-picoline>α-picoline>2,6-lutidine; the order was discussed in terms of the molecular complexes.
  • Kazuo Mukai
    1969 Volume 42 Issue 1 Pages 40-46
    Published: 1969
    Released: March 27, 2006
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    The results of static magnetic susceptibility measurements in the 1.8–300°K temperature range are reported on powder samples of the stable aromatic free radicals: 2,6-di-t-butyl-4(3,5-di-t-butyl-4-oxocyclohexa-2,5-dienylidene methyl) phenoxyl (Galvinoxyl) and 2,6-di-t-butyl-4(3,5-di-t-butyl-4-oxocyclohexa-2,5-dienylidene amino) phenoxyl (BIP) radicals. The susceptibility of Galvinoxyl follows the Curie-Weiss law above Tc=81±1°K, depending on the sample, with a Weiss constant of 11±3°K. However, at Tc=81°K, χp rapidly decreases, and below 66°K the susceptibility again increases, with different spin concentrations for independently-prepared samples as the temperature is lowered. A maximum at 81°K was also found by the EPR measurements; the anomaly of the susceptibility at this temperature is probably due to a first-order phase transition induced magnetically, accompanying the pairing of magnetic spins, judging from the results of differential thermal analysis and the magnetic susceptibility measurements. On the other hand, the magnetic susceptibility of the BIP radical exhibits a broad maximum at 54±2°K. This susceptibility can be explained approximately using a model which consists of a singlet ground state and a triplet state lying slightly above the ground state.
  • Osamu Kikuchi
    1969 Volume 42 Issue 1 Pages 47-52
    Published: 1969
    Released: March 27, 2006
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    A theoretical treatment of the H2NO radical is presented. In the calculation, the approximate SCF method of Longuet-Higgins and Pople for open-shell molecules is applied to the valence electron system, the CNDO/2 approximation is adopted, and the molecular excited states are approximated by linear combinations of some doublet Slater determinants constructed by means of the SCF MO for the ground state. The results thus obtained for the electronic structure of the H2NO radical are discussed. The calculated spectrum for the H2NO radical shows that the longest wavelength band has the n→π* character, and the π→π* transition energy is smaller than that for the n→σ* transition. The π→π* transition energy, 5.77 eV, calculated by the method in which only the π-electrons were explicitly considered, indicated that the π→π* band falls into the area near 240 mμ. From the calculated results for the H2NO radical and the solvent effect on the absorption bands of aliphatic nitric oxide radicals, two bands, at 450 mμ, and 240 mμ, characteristic of the latter radicals have been assigned to the n→π* and π→π* transitions respectively.
  • Haruo Shizuka
    1969 Volume 42 Issue 1 Pages 52-57
    Published: 1969
    Released: March 27, 2006
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    The photochemical primary processes of acetanilide have been discussed on the basis of the quantum yields in various solvents, the dependences of the quantum yields on the excitation wavelength, and the emission spectra. The quantum yields of the products (o-aminoacetophenone and p-aminoacetophenone) at 2537 Å decreased greatly in polar solvents. A non-linear relationship between the quantum yield and the fraction of hydrogen-bonded acetanilide in the cyclo-hexane-ethanol solution was obtained. No variation in the quantum yield was observed upon the change of the excitation from 2537 to 2740 Å. These results indicate the occurrence of a radiationless internal conversion, S1(ππ*)←S2(ππ*). The relative fluorescence intensity in a polar solvent was larger than that in a nonpolar solvent. On the basis of these studies, it can reasonably be considered that the primary process in the photochemical reaction of acetanilide involves predissociation.
  • Haruo Shizuka
    1969 Volume 42 Issue 1 Pages 57-65
    Published: 1969
    Released: March 27, 2006
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    The photochemical secondary processes of acetanilide have been studied. The photochemical reaction of p-methylacetanilide at 2537 Å did not produce the p-rearrangement product, but the o-rearrangement one. The quantum yields of the o-rearrangement and of the disappearance of p-methylacetanilide were 0.092 and 0.12 respectively. Comparing the quantum yields of acetanilide with those of p-methylacetanilide, the values of the quantum yields for the predissociation of the N–C bond, the back reaction, and the recombination ratio were estimated to be 0.25, 0.10, and 0.9 respectively. These results indicate that the recombination reaction between the pair radicals formed by the predissociation of the N–C bond occur efficiently in a solvent cage. The rate constants of the back reaction, the o-rearrangement, and the p-rearrangement were proportional to the odd π electron densities of the anilino radical. No intermediate was observed by the flash photolysis. The small dependence of the quantum yields of acetanilide on the temperature supports the predissociation mechanism previously described. On the basis of these studies, the mechanism of the photochemical reaction of acetanilide in the liquid phase has been proposed.
  • Sin-ichiro Kita, Ken-ichi Fukui
    1969 Volume 42 Issue 1 Pages 66-70
    Published: 1969
    Released: March 27, 2006
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    In order to understand the mechanism of the photosensitized, stereospecific cyclization of 3-methylene-1,5-heptadiene, we calculated the electronic state of two intermediates (13 imaginary conformations) by the extended Hückel molecular orbital method and discussed its rotation angle dependency. We obtained the following conclusions. 1) In the two intermediates, the second model (we suppose this to be more like a real intermediate) has lower energy than the first model (we suppose this to be an initial intermediate) both in the ground state and the excited state. 2) If it is necessary for this cyclization that an overlap stabilization exists between two carbon atoms to be bonded and the intermediate has lower energy in that state, the intermediate seems to cyclize after the transition to the ground state singlet. 3) The overlap stabilization between two carbon atoms mentioned above is mainly defined by the interaction between 2p electrons in the highest occupied orbital. This fact coincides with the consequence of the frontier electron theory. 4) The existence of the overlap stabilization between 2p electrons mentioend above corresponds to the fact that the special valence atomic orbital of that two carbon atoms has the same symmetry. This fact is in line with the Woodward-Hoffmann rule on “electrocyclic reactions.”
  • Yôichi Iida
    1969 Volume 42 Issue 1 Pages 71-75
    Published: 1969
    Released: March 27, 2006
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    The present paper deals with crystalline TCNQ, anion radical “simple” salts of M+ TCNQ\divdot, where M+ represents a diamagnetic counter cation. Their crystalline electronic spectra were measured in the range between 4.0 and 30.8 kK by means of diffuse reflectance. The crystalline spectra thus obtained were quite different from that of the TCNQ, radical anion monomer and exhibited a broad and intense low-energy band around 9 kK in the low-conductivity compounds and at 4.3 kK in the high-conductivity compound. These bands were ascribed to inter-radical charge-transfer in the solid state. The crystalline spectra were found to be closely correlated to their unusual electrical and magnetic properties. It was concluded that these physical properties were based on a unique TCNQ molecular arrangement in groups of several or an infinite number of face-to-face molecular systems.
  • Teijiro Yonezawa, Hiroko Yamabe, Hiroshi Kato
    1969 Volume 42 Issue 1 Pages 76-83
    Published: 1969
    Released: March 27, 2006
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    Molecular orbital investigations of the electronic structures of lone pairs of some azine compounds and quinones are carried out by the Hückel method and the extended Hückel method for σ and π electron systems. The delocalization and the s–p mixing of lone pairs are investigated. Qualitative discussions of the splitting of the lone-pair levels and the calculated n* transitions of these compounds are made. It is revealed that the Hückel method, which does not include direct interactions, gives an incorrect prediction for the symmetry of the energy levels of pyridazine. After comparative discussions, it is concluded that the lone paris couple with each other directly “through-space” as well as “through-bond.”
  • Hisae Enokido, Takako Shinoda, Yo-ichiro Mashiko
    1969 Volume 42 Issue 1 Pages 84-91
    Published: 1969
    Released: March 27, 2006
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    Heat capacities, latent heats and vapor pressures of solid and liquid neopentane were measured and the following values were obtained; heat of transition=628.7±0.3 cal/mol, T(trans. pt.)=140.498±0.05°K, heat of fusion=740.0±0.3 cal/mol, T(triple pt.)=256.750°K, and P(triple pt.)=268.47±0.13 Torr. The amount of impurity in the sample after purification was estimated from a plot of the equilibrium temperature against the reciprocal of the fraction melted. From the result the impurity present was found to be 0.0032 mol%. Despite of high purity, Cp value in the region below the melting point increases unexpectedly with temperature. This is interpreted as an effect of formation of vacancies in the crystals. The enthalpy required to form vacancies was estimated to be 3240±220 cal/mol from the analysis of the heat capacity curve in the region below the melting point. The molal entropy of the ideal gas at the boiling point, calculated from the calorimetric data, was 71.24±0.3 e. u. To bring this value into agreement with the value calculated from the infrared and Raman frequencies and the moments of inertia, requires the assumption of three equal potential energy maxima of 4.4 kcal/mol for hindered internal rotation of the methyl groups.
  • Noritake Yasuoka, Nobutami Kasai, Masao Kakudo
    1969 Volume 42 Issue 1 Pages 91-101
    Published: 1969
    Released: March 27, 2006
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    The crystal structure analysis of N-(p-methoxyphenyl-3-propyl)-p-bromobenzamide was carried out by means of X-rays. This compound crystallizes in two crystalline polymorphs, both belonging to the monoclinic system.
    α-form:a=14.592,b=9.572,c=11.242Å,β=94.26°;Z=4;space groupP21c
    β-form:a=11.940,b=10.019,c=6.577Å,β=90.56°;Z=2;space groupP21.
    A little difference in structure is observed between the molecules in the two polymorphs, while the conformations of the carbon-carbon bonds in the 3-aminopropyl group are of the trans form. In both forms, belts of molecules parallel to the b axis are formed by hydrogen bonds between the amide groups of the molecules related by the twofold screw axis. These belts are packed anti-parallel in the α-form, but parallel in the β-form.
  • Masamichi Tsuboi, Katsuichi Shuto, Shosuke Takemura, Susumu Nishimura
    1969 Volume 42 Issue 1 Pages 102-107
    Published: 1969
    Released: March 27, 2006
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    Infrared absorptions have been observed in the 1800–700 cm−1 region of four purified amino-acid transfer ribonucleic acids (tRNA’s): alanine tRNA and valine-I tRNA from Torulopsis utilis (torula yeast) and methionine tRNA and tyrosine tRNA from Escherichia coli in their deuterated film. Spectral features in the 1550–1750 cm−1 region of the valine, methionine, and tyrosine tRNA’s indicate that each of these tRNA’s has an amount of base-pairs, which is in accord with the “clover leaf” structure previously proposed. The relative amounts of the paired and unpaired cytosine residues are estimated on the assumption that the intensity ratio of the 1523 and 1500 cm−1bands is 0.18 for the paired cytosine residue and 0.84 for the unpaired cytosine residue. The results are also compatible with the “clover leaf” structure.
  • Takeshi Ito, Takehiko Chiba
    1969 Volume 42 Issue 1 Pages 108-116
    Published: 1969
    Released: March 27, 2006
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    Deuteron quadrupole coupling tensors in Co(ND3)6Cl3 were determined at various temperatures. The observed quadrupole coupling shows that Co(ND3)63+ ions execute a rapid isotropic reorientation at high temperatures (above 320°K for one of the sites (the 4f sites) and above 190°K for another (the 2e sites), while at low temperatures (below 190°K for the 4f sites, and 170°K for the 2e sites), only a C3 axis reorientation of the ligand ND3 groups is present. The deuteron resonance spectra clearly show that Co(ND3)63+ ions in the 4f sites begin to reorient about one of the three C4 axes at intermediate temperatures (about 240°K). On the basis of the orientation of quadrupole tensors, probable orientations of Co(ND3)63+ ions in the 4f sites in the crystal are proposed. Additional measurements of the proton resonance on a single crystal of Co(NH3)6Cl3support the results obtained from the deuteron resonance. To obtain the reorientation rates and the activation energies of these reorientational motions, the deuteron resonance line width at the 4f sites is measured at various temperatures and at various crystal orientations. From the temperature dependence of the line width, the presence of two cations with slightly different rates at the 4f sites is suggested. However, because of the limits set by the various experimental conditions, reliable values of the reorientation rates and activation energies could not be obtained.
  • Masaru Nishikawa, Kazufumi Kuroda, Niro Matsuura
    1969 Volume 42 Issue 1 Pages 116-118
    Published: 1969
    Released: March 27, 2006
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    The effect of additives and density on the radiolysis of ammonia at 140°C was studied over the density range 0.07 to 0.13 g/cc. The observation of a sharp decrease of G values in the radiolysis of pure ammonia at d∼0.1 g/cc confirmed the result reported by Toi et al. (Radiation Res., 17, 399 (1962)). The yield of hydrogen in the presence of ∼1.5 mol% C3H6 was practically independent of density at G=0.65 over the density range studied. G(H2) in the presence of C3H8, estimated by extrapolation to zero propane concentration, was also constant at G\simeq5.7 at d\simeq0.07 and 0.13 g/cc. These observations were discussed in relation to the mechanism for depression of G values in the radiolysis of pure ammonia at higher densities.
  • Kiyoshi Yamasaki, Jinsai Hidaka, Yoichi Shimura
    1969 Volume 42 Issue 1 Pages 119-126
    Published: 1969
    Released: March 27, 2006
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    Four cobalt(III) complexes of the tris-chelate type containing two dicarboxylate anions and one aminocarboxylate anion have been newly prepared and separated into their optical isomers by a chemical resolution method: they are bismalonatoglycinato-, bismalonato(L-alaninato)-, bisoxalato(L-alaninato)- and bisoxalato(β-alaninato)-cobalt(III) complexes. The diastereomeric isomers of bisoxalato(L-alaninato)cobalt(III) complex have also been separated by the solubility difference between their barium salts. The absorption spectra, circular dichroism spectra and rotatory dispersion of these complexes have been measured and discussed in relation to the splitting of the d–d transition bands. The absolute configurations of the complexes have been inferred from their circular dichroism spectra. The additivity of configurational and vicinal contributions to the optical activity has been substantiated for the bisoxalato- and bismalonato-(L-alaninato)-cobalt(III) complexes, and some considerations concerning the less stereospecific formation of the L-alaninato diastereomeric isomers have been made in relation to the additivity.
  • Tomio Onishi
    1969 Volume 42 Issue 1 Pages 127-131
    Published: 1969
    Released: March 27, 2006
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    Tetrafluoroborate ions (BF4) can be formed only in a strongly acid solution. Certain acid thermal waters and volcanic gases in the active volcanic zone can be expected to be the media of BF4 formation. When BF4 is supplied to natural waters, its rate of hydrolysis is relatively low, suggesting the possibility of the occurrence of BF4 in natural waters. The contents of BF4 have been determined in various thermal water samples from a volcano in Satsuma Iwo-jima, and the presence of BF4 confirmed. The BF4 content in the condensed water of volcanic gas from a fumarole with the high temperature of 745°C is 304 mg/l, which is 26% of the total F, and 79% of the total B content. The BF4 content in a sample of water from Kitabira Spa (pH 1.1) is 8.0 mg/l, which is about 50% of the total F or B. However, the presence of BF4 can not be confirmed in ordinary natural waters such as land and sea waters.
  • Shoichiro Yamada, Akira Takeuchi, Kuniko Yamanouchi, Katsumoto Iwasaki
    1969 Volume 42 Issue 1 Pages 131-136
    Published: 1969
    Released: March 27, 2006
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    Many new nickel(II) and copper(II) complexes (abbreviated as M(X-sal.R)2) of Schiff bases were obtained from C-substituted salicylaldehydes and 2,6-dimethyl- and 2,6-diethyl-aniline, where X denotes 5-Br, 5-Cl, 5,6-benzo, 5-NO2 and 3-CH3O. For X=5-Cl, the corresponding nickel(II) complex with R=2,6-dichlorophenyl was also synthesized. All these nickel(II) complexes consist of square-planar molecules in the solid state and in non-donor solvents. The nickel (II) complexes, when dissolved in pyridine, either take up two pyridine molecules to form six-coordinated complexes or retain the original planar configuration. The configuration in pyridine depends upon the nature of X, demonstrating that the effect of X on the electronic state of the ligand may also be important, besides the steric factor, in determining the configuration of the nickel(II) complexes. The corresponding copper (II) complexes, which are square-planar in the solid state and in non-donor solvents, combine with one or two pyridine molecules, when dissolved in pyridine.
  • Hiroshi Kawaguchi, Naomichi Yano, Shinichi Kawaguchi
    1969 Volume 42 Issue 1 Pages 136-140
    Published: 1969
    Released: March 27, 2006
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    Several diacidobis(trimethylenediamine)cobalt(III) complexes including nitrate, nitrite and thiocyanate ions as ligands have been prepared by ligand substitution reactions of trans-dichlorobis(trimethylenediamine)cobalt(III) chloride in methanol. All these compounds were assumed to have the trans configuration according to the Baldwin’s criterion based on the CH2 rocking vibration. Isomeric pairs of chloronitro and chloronitrito complexes were also characterized by means of infrared data.
  • Taitiro Fujinaga, Kosuke Izutsu, Takeo Adachi
    1969 Volume 42 Issue 1 Pages 140-145
    Published: 1969
    Released: March 27, 2006
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    The solubility and polarographic behavior of dissolved oxygen have been investigated in air-saturated DMSO-water mixtures at 25°C and 45°C. The first oxygen wave, which corresponds to one-electron reduction to superoxide ions in water-poor DMSO solutions of 0.1 M Et4NClO4, changes to a two-electron process in the range of water content between 10 and 30% because of the protonation reaction due to water. The rate of protonation is potential-dependent. The rate also depends on the species and the concentrations of the supporting electrolytes. The temperature effect is small. Using the solubility and polarographic data obtained, the polarographic diffusion coefficients of oxygen in the mixed solvent have been calculated.
  • Yoichi Sasaki, Junnosuke Fujita, Kazuo Saito
    1969 Volume 42 Issue 1 Pages 146-152
    Published: 1969
    Released: March 27, 2006
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    New binuclear cobalt(III) complexes, (−)D-[(l-pn)2Co(μ-NH2,O2)Co(l-pn)2](NO3)4·3H2O, (+)D-[(l-pn)2Co(μ-NH2,O2)Co(l-pn)2]I3·6H2O, (+)D-[(l-pn)2Co(μ-NH2,NO2)Co(l-pn)2]Br4·6H2O, (+)D-[(l-pn)2Co(μ-NH2,OH)Co(l.pn)2](NO3)4·2H2O and (−)D-[(l-pn)2Co(μ-NH2,SO4)Co-(l-pn)2](NO3)3 were prepared and their absolute configurations determined to be ΛΛ on the consideration of the stereospecific coordination of l-propylenediamine (l-pn) to the metal ion. On the basis of these identifications, absolute configurations of the corresponding ethylenediamine-(en) complex ions were assigned. The nature of the d–d bands of these polynuclear complexes seems to be very similar to those of uninuclear cobalt(III) complexes. One of the two central cobalt(III) ions is regarded as a member of an asymmetric chelate ligand to the other cobalt ion, and the CD corresponding to the d–d bands appears to depend mainly on the strength of vicinal effect due to such a chelate ring.
  • Shoichiro Yamada, Yoshio Kuge
    1969 Volume 42 Issue 1 Pages 152-156
    Published: 1969
    Released: March 27, 2006
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    Many new oxovanadium(IV) complexes (abbreviated as VO(X-sal.R)2) of Schiff bases obtained from substituted salicylaldehydes and alkylamines have been synthesized as crystals, where X=H and 3-CH3O and R=CH3, C2H5, n-C3H7, n-C4H9, iso-C3H7, CH(CH3)(C2H5), CH2CH-(CH3)2 and cyclohexyl. Since all these complexes show similar electronic spectra, it is considered that they take an essentially similar configuration, that is, a square-pyramidal one in the solid state and in chloroform, even for R=α-branched alkyls. This result is different from that of the copper (II) complexes. It is also concluded that these oxovanadium(IV) complexes, when dissolved in pyridine, take up one pyridine molecule to form a six-coordinated species. The configuration of the pyridine solvate depends upon R.
  • Isao Masuda, Motonori Tamaki, Koichiro Shinra
    1969 Volume 42 Issue 1 Pages 157-162
    Published: 1969
    Released: March 27, 2006
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    Through reaction with nitric oxide, divalent Ni, Cu, and Pd complexes of bis(acetylacetone)-ethylenediimine have been shown to yield fine crystalline compounds of the general formula M(C12H17N3O3), where M=Ni or Cu, and of M(C12H16N4O4) where M=Ni, Cu or Pd, depending on experimental conditions. They are insoluble in water. The former compounds are rather soluble in common organic solvents, but the latter are sparingly soluble, except in pyridine. On the basis of analytical data and IR-spectral analyses, they are thought not to be nitrosyl metalcomplexes but oxime type complexes.
  • Mutsuo Kodama, Chifumi Sasaki, Katsumi Miyamoto
    1969 Volume 42 Issue 1 Pages 163-168
    Published: 1969
    Released: March 27, 2006
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    The substitution reactions of Eriochrom Black T (BT) with cobalt(II) and nickel(II) chelates of 1,2-diaminocyclohexanetetraacetic acid (CyDTA) and of diethylenetriaminepentaacetic acid (DTPA) were studied spectrophotometrically. The reactions of BT with CyDTA and DTPA chelates of these metal(II) ions were found to have the same reaction mechanism as the reactions with EDTA chelates did, but to be considerably slower than the latter reactions. On the basis of a comparison of the observed rate constants with those calculated on the basis of the proposed reaction mechanism (glycinate intermediate), the steric effect due to the cyclohexane ring in the CyDTA or –CH2–CH2–N(CH2–COO)–CH2–CH2–N(CH2–COO)2 group in DTPA on the reaction rate was discussed in a quantitative manner. The effect due to the former group was estimated to be smaller than that due to the latter group.
  • Takashi Komorita, Jinsai Hidaka, Yoichi Shimura
    1969 Volume 42 Issue 1 Pages 168-177
    Published: 1969
    Released: March 27, 2006
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    Planar bis-type complexes of copper(II) with L-leucine-, L-valine-, L-phenylalanine- and L-proline-amidate ligands have been newly synthesized and characterized mainly spectroscopically together with the known complexes with glycine- and L-alanine-amidates. The geometrical structures of these [Cu(N)4]-type complexes have been tentatively determined. The blue colored complexes, Cu(glycine-amide)2SO4 and its L-alanine amide analogue, have been isolated, too. The circular dichroism spectra of the complexes containing optically active ligands have been measured in various solvents and discussed in comparison with the available data for square planar d8-complexes or for amino acidato complexes. A number of interesting relations were observed among the circular dichroism spectra of the copper(II) and the square planar d8 complexes with optically active bidentate ligands.
  • Shigeru Oae, Naomichi Furukawa, Takashi Asari
    1969 Volume 42 Issue 1 Pages 177-180
    Published: 1969
    Released: March 27, 2006
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    The mechanism of both the alkaline fusion and the alkaline hydrolysis of halophenols has been investigated. In case of alkaline fusion, the product identified is resorcinol, the formation of which has been found to proceed through the benzyne intermediate. While the alkaline hydrolysis of halophenols gives different ratio of dihydroxyphenol and phenol by changing the mole ratio of halophenol to alkali, by utilizing 14C tracer experiment and substituted halophenol, the mechanism of the formation of both products has been revealed to proceed by way of the direct substitution of halide with hydroxide. Copper compounds are found to be effective in this reaction.
  • Otohiko Tsuge, Masashi Tashiro, Ichiro Shinkai
    1969 Volume 42 Issue 1 Pages 181-185
    Published: 1969
    Released: March 27, 2006
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    The reactions of acenaphthenequinone (III) with several Wittig reagents have been studied. When III was reacted with equimolar amounts of benzylidenetriphenylphosphoranes (IV) at room temperature, the corresponding benzylideneacenaphthenones (V) were obtained in fairly good yields, but the reactions of benzil and phenanthrenequinone with IV did not take place under similar conditions. The reaction of III with two equivalents of IV under severe conditions afforded only V, and no dibenzylidene compounds were obtained. The reaction of III with resonance-stabilized phosphoranes, such as acetonylidene-, phenacylidene- and p-chlorophenacylidenephosphoranes, afforded the expected α,β-unsaturated ketones. In the reaction with ethoxycarbonylmethylenephosphorane, two stereo-isomeric ethoxycarbonylmethyleneacenaphthenones, which were also obtained from the reaction with diethyl ethoxycarbonylmethylphos-phonate, were formed. The structures of the isomers were confirmed on the basis of NMR, UV, and mass spectral studies. Methylenephosphorane reacted with III to give methyleneacena-phthenone in a poor yield. On the contrary, the reaction with ethylidenephosphorane gave bis-2,2′-methyleneacenaphthenone, which was also formed by the reaction of acenaphthenone with glyoxal, in a good yield.
  • Otohiko Tsuge, Ichiro Shinkai, Masashi Tashiro
    1969 Volume 42 Issue 1 Pages 185-190
    Published: 1969
    Released: March 27, 2006
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    The reactions of benzylideneacenaphthenones with hydrazines are reported. The reaction of benzylideneacenaphthenone with hydrazine hydrate in methanol at 40°C gave 1-hydroxy-2-hydrazinobenzylacenaphthylene, which was then cyclized to the 1-acetylpyrazoline by treating it with acetic anhydride. The hydrazino compound reacted with phenyl isocyanate to give the 1:2-adduct, which, when then treated with hydrochloric acid, suffered ring closure to the pyrazoline compound. Under severe conditions with hydrazine hydrate, however, the reductive cleavage reaction took place, giving the hydrazones of both acenaphthenone and benzaldehyde. Similar phenomena were also observed in the reaction with p-substituted benzylideneacenaphthenones. On the other hand, the reaction with phenylhydrazines in ethanol containing sulfuric acid afforded directly the expected pyrazolines, from which pyrazoles were then prepared by treating them with lead tetraacetate. Furthermore, the corresponding pyridazine was formed in the reaction of phenacylideneacenaphthenone with hydrazine hydrate, while the reaction with 2,4-dinitrophenyl-hydrazine gave the pyrazoline compound.
  • Chung-gi Shin, Yasuhiro Chigira, Mitsuo Masaki, Masaki Ohta
    1969 Volume 42 Issue 1 Pages 191-193
    Published: 1969
    Released: March 27, 2006
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    Treatment of the ester of 2-(2-chloroacetamido)-2-alkenoic acid with ammonia led to the formation of 3-alkylidene-2,5-piperazinedione. By using this method, total synthesis of albonoursin was accomplished. 2-(2-Chloroacetamido)-4-methyl-2-pentenoic acid, derived from the condensation of 4-methyl-2-oxopentanoic acid with chloroacetonitrile or the pyrolysis of 2,2-bis(2-chloroacetamido)-4-methylpentanoic acid, was converted to the ethyl ester, which was treated with ammonia to give 3-isobutylidene-2,5-piperazinedione. The piperazinedione was also synthesized by the esterification of 2-(2-aminoacetamido)-4-methylpentenoic acid, followed by a cyclization of the ester. Condensation of the piperazinedione with benzaldehyde yielded 3-benzylidene-6-isobutylidene-2,5-piperazinedione, and its physical constants are virtually identical with those recorded for the natural albonoursin.
  • Mitsuhiro Kinoshita, Hiroaki Yanagisawa, Shuhei Doi, Eisuke Kaji, Sumi ...
    1969 Volume 42 Issue 1 Pages 194-199
    Published: 1969
    Released: March 27, 2006
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    The reaction of substituted derivatives of α-nitrocinnamates bearing a nitro group or a chlorine atom at the p- or m-position with cyclopentadiene produced corresponding cyclic α-nitro esters(adducts) in a good yields. The reaction of ethyl α-nitrocrotonate with cyclohexadiene gave ethyl 3-methyl-2-nitrobicyclo[2.2.2]-5-octene-2-carboxylate. In the case of an adduct, ethyl 2-nitro-3-(p-nitrophenyl)bicyclo[2.2.1]-5-heptene-2-carboxylate, there could be isolated four diastereoisomers as crystalline forms by column chromatography and fractional recrystallization. The stereochemistry of the four isomeric adducts were established by NMR spectroscopy. The readily available three of those isomers were converted to corresponding pure isomers of amino acids by reduction followed by hydrolysis. From the other adducts the major amino acid isomers or the amino acid mixtures were obtained in an analogous route.
  • Kenji Fukui, Mitsuru Nakayama, Teruo Harano
    1969 Volume 42 Issue 1 Pages 199-202
    Published: 1969
    Released: March 27, 2006
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    2′-Carboethoxymethoxy-4′,5′-dimethoxy-7-hydroxyisoflavone was prepared from 7-benzyloxy-4′,5′-dimethoxy-2′-hydroxyisoflavone via the corresponding 2′-carboethoxymethoxyisoflavone. The hydrolysis of the 7-hydroxyisoflavone with dilute alkali gave tephrosic acid (2,4-dihydroxyphenyl 2-carboxymethoxy-4,5-dimethoxybenzyl ketone) in a good yield.
  • Yoshinobu Takegami, Yoshihisa Watanabe, Takeaki Mitsudo, Hiromitsu Mas ...
    1969 Volume 42 Issue 1 Pages 202-205
    Published: 1969
    Released: March 27, 2006
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    The reaction between potassium iron carbonylates (KHFe(CO)4, K2Fe(CO)4 and K2Fe2-(CO)8) and different olefin oxides has been studied. 1,2-Olefin oxides generally react with these carbonylates and carbon monoxide under an atmospheric pressure and at 30°C. This reduction gives the corresponding terminal olefins and the internal olefins which are formed from the 1-olefins by isomerization. Internal olefin oxides do not react with the carbonylates under the reaction conditions employed. The reduction reaction seems to compete with the carbonylation reaction. A mechanism for the reduction reaction is suggested.
  • Yoshinobu Takegami, Yoshihisa Watanabe, Hiromitsu Masada, Takeaki Mits ...
    1969 Volume 42 Issue 1 Pages 206-210
    Published: 1969
    Released: March 27, 2006
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    In the reaction of cobalt hydrocarbonyl with 1-pentene at 10°C, solvents have a great effect on the distribution of the products, caproylcobalt carbonyl (I) and α-methylvalerylcobalt carbonyl (II). The I-to-II ratio is 72 : 28 in toluene, in toluene-dioxane (1 : 1 in volume), and in tolueneethyl acetate. The percentage of II increases to 40–66% in toluene-diethyl ether, -tetrahydrofuran, -acetone, -ethyl alcohol, and -acetonitrile. In the hydroformylation of propylene, the distribution of the products, n- and isobutyraldehyde, is also affected by the solvents. In toluene, the n-to-iso ratio is about 75 : 25, while in dioxane and in butyl acetate the percentage of the n-aldehyde increases to 79–83%. In methyl alcohol, dimethyl acetals of the aldehydes and n- and isobutyrate are formed. The n-to-iso ratio is the highest in the esters (3.2–8.5), followed by the acetals (0.7–1.6) and the aldehydes (0.4).
  • Rikuhei Tanikaga
    1969 Volume 42 Issue 1 Pages 210-214
    Published: 1969
    Released: March 27, 2006
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    The mechanism of the photochemical reaction of nitrosobenzene (I) has been investigated. The irradiation of I leads to the formation of a phenyl radical and nitric oxide. The reaction of the phenyl radical with I yields diphenylnitroxide, which is then easily reduced to diphenylamine. The reaction of diphenylamine with the nitric oxide gives C-nitrosodiphenylamines, which are then photochemically oxidized to C-nitrodiphenylamines. On the other hand, I is oxidized to nitrobenzene and is, at the same time, reduced to azoxybenzene and azobenzene. Azoxybenzene is photochemically rearranged to 2-hydroxyazobenzene.
  • Hiroshi Suginome, Norio Sato, Tadashi Masamune
    1969 Volume 42 Issue 1 Pages 215-220
    Published: 1969
    Released: March 27, 2006
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    The results of photolysis of three fused cyclopentyl nitrites, Ib, VIIIb, XIV, all of which have 22,27-imino-17,23-oxidojervane framework, are described. In all three cases, competition among the reactions of 11-alkoxyl radical, which led to a variety of products, has been observed. However, the cleavage of α,β carbon-carbon bond to the nitrosoxyl group in these compounds is not the major course of the reaction. It has been found that whenever sterically possible (e. g., Ib), 11-alkoxyl radical in these nitrites is capable of achieving the Barton reaction and the reaction leads to relatively few products. In two cases of these photolyses, the reaction is accompanied by epimerization of the relevant alkoxyl radicals. Some aspects of these transformations are considered in the light of other available data.
  • Akio Sakurai, Hiroshi Midorikawa
    1969 Volume 42 Issue 1 Pages 220-223
    Published: 1969
    Released: March 27, 2006
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    Several heterocyclic compounds, such as dihydropyridine, pyridine, tetrahydroquinoline and hexahydroquinoline derivatives, were prepared by the reaction of benzoylacetonitrile with such ketones as acetone, cyclopentanone, cyclohexanone, alkylcyclohexanone, alkylidenecyclohexanone, and aromatic α,β-unsaturated ketone in the presence of ammonium acetate.
  • Yasuhiro Chigira, Mitsuo Masaki, Masaki Ohta
    1969 Volume 42 Issue 1 Pages 224-228
    Published: 1969
    Released: March 27, 2006
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    α-Ethoxy- and α-acetoxycinnamoyl chlorides were synthesized by treatments of α-ethoxy-and α-acetoxycinnamic acid with thionyl chloride and oxalyl chloride, respectively, and reactions of ammo acid esters with the cinnamoyl chlorides were investigated in order to seek for a synthetic method of N-(phenylpyruvoyl) amino acids. N-Hydroxy- or N-benzyloxy-DL-alanine esters prepared from 2-bromopropionic esters and hydroxylamine or benzyloxyamine were treated with α-ethoxycinnamoyl chloride to give the corresponding N-(α-ethoxycinnamoyl) derivatives. Treatment of L-leucine ethyl ester with α-acetoxycinnamoyl chloride afforded N-(α-acetoxycinnamoyl)-L-leucine ethyl ester, the removal of the acetyl group from which was readily accomplished under mild, basic conditions, and N-(phenylpyruvoyl)-L-leucine ester was obtained. Treatment of the ester with ammonia yielded 3-benzylidene-6-isobutyl-2,5-piperazinedione.
  • Yasuhiro Chigira, Mitsuo Masaki, Masaki Ohta
    1969 Volume 42 Issue 1 Pages 228-232
    Published: 1969
    Released: March 27, 2006
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    Treatment of N-benzyloxy-DL-alanine ethyl ester (I) with α-acetoxycinnamoyl chloride (II) gave N-(α-acetoxycinnamoyl)-N-benzyloxy-DL-alanine ethyl ester (III), which was treated with aqueous sodium bicarbonate, piperidine or hydroxylamine to afford N-benzyloxy-N-(phenyl-pyruvoyl)-DL-alanine ethyl ester (IV). Reaction of III or IV with ammonia afforded 5-benzylidene-2-methyl-4-oxo-2-imidazolidinecarboxylic acid (V), which was transformed into 5-methyl-4-phenyl-2,3-pyrrolidinedione (VI) by treatment with aqueous sodium hydroxide and into methyl 5-benzylidene-2-methyl-4-oxo-2-oxazolidinecarboxylate (VII) by treatment with methanolic hydrogen chloride. VI was also derived from III or IV by treatment with sodium hydroxide. N-(α-Acetoxycinnamoyl)-N-hydroxy-DL-alanine t-butyl ester prepared from N-hydroxy-DL-alanine t-butyl ester and II, was treated with aqueous sodium hydroxide to give t-butyl 5-benzylidene-2-methyl-4-oxo-2-oxazolidinecarboxylate.
  • Kenji Fukui, Mitsuru Nakayama, Teruo Harano
    1969 Volume 42 Issue 1 Pages 233-236
    Published: 1969
    Released: March 27, 2006
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    7,2′-Dihydroxy-4′,5′-dimethoxyisoflavone was obtained from 7-hydroxy-2′,4′,5′-trimethoxyisoflavone by selective demethylation with aluminum chloride in acetonitrile. By partial benzylation, the dihydroxyisoflavone then gave 7-benzyloxy-4′,5′-dimethoxy-2′-hydroxyisoflavone. The subsequent treatment of the latter with sodium borohydride afforded 3-hydroxy-8,9-dimethoxypterocarpan via its 3-benzyloxy-compound.
  • Hiromu Imai, Tadahiko Yamada
    1969 Volume 42 Issue 1 Pages 237-240
    Published: 1969
    Released: March 27, 2006
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  • Yoshiharu Izumi, Masami Imaida, Tadao Harada, Tadashi Tanabe, Shinichi ...
    1969 Volume 42 Issue 1 Pages 241-243
    Published: 1969
    Released: March 27, 2006
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  • Takeaki Iida, Hiroshi Nozaki
    1969 Volume 42 Issue 1 Pages 243-244
    Published: 1969
    Released: March 27, 2006
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  • Toru Nozaki, Osamu Hiraiwa, Chujiro Henmi, Kunji Koshiba
    1969 Volume 42 Issue 1 Pages 245-247
    Published: 1969
    Released: March 27, 2006
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  • Takeo Saegusa, Takashi Ueshima, Sadao Kitagawa
    1969 Volume 42 Issue 1 Pages 248-250
    Published: 1969
    Released: March 27, 2006
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  • Kikumasa Sato, Masao Hirayama, Takashi Inoue, Shoji Kikuchi
    1969 Volume 42 Issue 1 Pages 250-252
    Published: 1969
    Released: March 27, 2006
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  • Atsushi Mizuike, Nobuhiko Mitsuya, Kunio Yamagai
    1969 Volume 42 Issue 1 Pages 253-255
    Published: 1969
    Released: March 27, 2006
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