Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 42 , Issue 3
Showing 1-50 articles out of 69 articles from the selected issue
  • Takehiko Watanabe, Takeshi Mineshita, Sôzaburo Ono
    1969 Volume 42 Issue 3 Pages 583-593
    Published: 1969
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Dependence of the viscosity of the polyvinylpyrrolidone (\barMv=4.0×104 and 9.0×105) solutions on the bore-size of capillary viscometer has been studied at 35°C, in pure water, in dimethyl sulfoxide (DMSO), in water-DMSO, and in aqueous solution with various cosolutes, at various concentrations (0.5–5.0 g/100 ml). Viscosity measurements were carried out with a Maron-Belner type low shear capillary viscometer with various capillary radii (0.0190–0.0761 cm) within the shear stress range of 0.2–20 dyn/cm2 at the capillary wall. The solutions showed a behavior of non-Newtonian flow and dependence on the size of the capillary. The viscosity of the polymer solutions in DMSO, and in water-DMSO decreased with the decrease in the capillary bore-size within the range of shear stress studied, and that in pure water, although similar phenomena as above were observed in higher shear stress, increased with the decrease in the capillary bore-size at the range of the lower shear stress, and this capillary bore-size dependence could not be observed with the aqueous solutions with cosolutes. The difference in the characteristics of the capillary bore-size dependence of the viscosity may be attributed to the difference in the behavior of the polymer molecules existing near the wall at which the thermal motion of the polymer molecules will be hindered by the existence of the capillary wall. The results were represented by the modified Ree-Eyring generalized flow formula for a flow system containing one Newtonian flow unit and one non-Newtonian one which included the additional terms dependent on the capillary bore-size. The viscosity equation suitable for analysing the dependence of the viscosity on the capillary bore-size at entire ranges of the rate of shear, was derived by assuming the wall layer composed of the double layers (of thickness do and dido) in the flowing liquid in the capillary tube, and by combining this equation with the modified Ree-Eyring equation, the values of do and di were calculated.
  • Takeshi Mineshita, Shigeru Matsumura, Hiromi Ono, Takehiko Watanabe, S ...
    1969 Volume 42 Issue 3 Pages 594-599
    Published: 1969
    Released: March 27, 2006
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    Dependence of the viscosity of the solution of γ-polyglutamic acid in eater at various pH’s on the bore-size of the capillary viscometer has been studied at 25°C at various concentrations (0.01–0.05 g/100 ml). Measurements were carried out with a Maron-Belner type low shear capillary viscometer with various capillary radii (1.9×10−2–7.6×10−2cm) within the shear stress range 0.2–20 dyn/cm2 at the capillary wall. The polymer solutions showed a non-Newtonian flow behavior and a capillary bore-size dependence and both of these properties were diminished with the decreasing of pH. This capillary bore-size dependence may be attributed to the geometric hindrance of the capillary wall to the thermal motion of the polymer molecules near the wall. The dissolved state of the polymer molecules in solutions of various pH’s has been studied by means of optical rotatory dispersions, flow birefringence and intrinsic viscosity. The dissolved state of the polymer solution as well as the capillary bore-size dependence were sensitive to pH. The polymer molecule in neutral and alkaline media may be in the form of a highly expanded chain and in acid medium in a contracted form having a some ordered chain conformation.
  • K. C. Gupta, M. P. Singh
    1969 Volume 42 Issue 3 Pages 599-607
    Published: 1969
    Released: March 27, 2006
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    The reaction rate is independent of the concentration of ferricyanide ion and directly proportional to both the reducing sugar and ammonia concentration. The reaction is of general basic catalysis in nature. The reaction rate is decreased with the addition of ammonium chloride due to common ion effect. The catalytic constants kOH and kNH3 have been calculated graphically. The reaction rate is, also, decreased with the gradual decrease in dielectric constant of the solvent and increased with the gradual increase in ionic strength. The rate expression obtained is as:
    (Remark: Graphics omitted.)
  • Satoru Tsuda, Akira Yokohata, Michihiro Kawai
    1969 Volume 42 Issue 3 Pages 607-614
    Published: 1969
    Released: March 27, 2006
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    The negative ion mass spectra of nitroalkanes (nitromethane, nitroethane, 1-nitropropane and 2-nitropropane) have been mesaured with a mass spectrometer under electron energies of 80 eV, 40 eV, 9.5 eV and 4.5 eV in the range of pressure used for usual analysis. The spectral intensities of negative ions were compared with those of positive ions. In 80 or 40 eV electron impact experiments, m/e 16 (O), 46 (NO2), 26 (probably, CN) and 42 (probably, CNO or C2H4N) ions were commonly found. Their yields showed good linearity against pressure under the present experimental conditions. The peaks of m/e 61 (parent ion; CH3NO2) in nitromethane, of m/e 25 (C2H) in nitroethane, 1-nitropropane and 2-nitropropane, and a relatively strong peak of m/e 60 (CH2NO2) in 1-nitropropane were characteristic. For lower electron energies, the strong dependency of the yield of negative ions on the electron energy was confirmed. The yield of negative ions as compared with positive ions for 80 eV and 40 eV of electron energy was lower by a factor of ∼104. On the other hand, the comparison of the yield of positive ions for 15 eV electrons with that of negative ions for 9.5 eV electrons gave the value of ∼0.2. In addition, of the role these negative ions in radiolysis has been briefly discussed.
  • Satoru Tsuda, Akira Yokohata, Michihiro Kawai
    1969 Volume 42 Issue 3 Pages 614-618
    Published: 1969
    Released: March 27, 2006
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    The ionization efficiency (IE) curves of NO2, O and CH2NO2 ions from nitroalkanes (nitro-methane, nitroethane, 1-nitropropane and 2-nitropropane) have been measured with a Hitachi RMU-6D mass spectrometer. Based on each authorized value of IP(CH3, C2H5, C3H7, O and H), D(C–NO2, C–H, C–C, NO–O and N–O), EA(NO2 and O) and the excitation energy of CH3, the respective onsets observed for the electron energies above ∼3 eV on the IE curves were suggested to be interpreted as appearance potentials of the following reactions. For NO2 ions, RNO2+e→R*+NO2, RNO2+e→R+NO2+e; for O ions, RNO2+e→RNO+O, RNO2+e→RN+O+O, RNO2+e→RN++O+O+e;for CH2NO2 ions, CH3NO2+e→H+ CH2NO2+e, RNO2+e→H+R1+CH2NO2. On the other hand, the strong peak of NO2 ions due to the dissociative electron capture process (RNO2+e→R+NO2) was observed at the lower electoron energy. Furthermore, a value of EA(CH2NO2) was presented to be ∼0.5 eV.
  • Toyozo Uno, Katsunosuke Machida, Kazuhiko Hanai, Yutaka Saito
    1969 Volume 42 Issue 3 Pages 619-624
    Published: 1969
    Released: March 27, 2006
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    The infrared spectra of seven monoacylureas and their NN′-deuterated compounds have been measured in the region between 3600 and 450 cm−1. A number of characteristic absorption bands of the –CONHCONH2 and –CONDCOND2 groups have been found and assigned by referring to the infrared spectra of related compounds and the isotopic frequency shifts. Partial deuteration by mixtures of water and heavy water has been made to distinguish the absorptions due to the NH and NH2 groups from each other. The features of infrared spectra of monoacylureas can be explained by regarding them as composite spectra of aliphatic imides and urea. From the effect of the alkyl frame-work vibrations for the imide III frequency, it is suggested that the RCONH– group of monoacylureas takes the trans conformation.
  • Akira Kira, Masao Koizumi
    1969 Volume 42 Issue 3 Pages 625-630
    Published: 1969
    Released: March 27, 2006
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    A transient species characterized by the absorption peaks at 350 mμ and 560 mμ has been found in the flash photolysis of acridan in both benzene and methanol solutions. This species has been proved to be different from the acridine semiquinone reported already, but has been identified as another acridine semiquinone radical on the basis of its direct conversion to acridine and also from its low reactivity to oxygen which denies the possibility of being triplet acridan. Thus it is concluded that two isomeric forms of acridine semiquinone exist. From the result of the flash photolysis of biacridan, the one reported previously has been identified definitely with a radical having a hydrogen atom attached to the nitrogen atom of acridine. Therefore, the newly discovered one is most likely a radical with a hydrogen atom attached on the 9 carbon atom of acridine.
  • Hiroshi Sumitomo, Ichiro Takemura
    1969 Volume 42 Issue 3 Pages 631-634
    Published: 1969
    Released: March 27, 2006
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    It was found that N-vinylcarbazole (VCZ) initiated the polymerization in the presence of β-cyanoacrolein (CAL) even in air at room temperature. The polymerization of VCZ induced by CAL was investigated in benzene at 60°C. Polymer formed was found to be VCZ homopolymer. The rate of polymerization attains to a maximum at the mole fraction of CAL of about 0.65 in the monomer mixture. The products obtained from the terpolymerization in the system of CAL-VCZ-Styrene in benzene at 60°C contain no CAL unit and exclusively consist of the VCZ component. The composition curve of the copolymer is contrasted with that of a radical initiated copolymer. In view of these results, as well as the Q-e values of both CAL and VCZ, it seems possible that the cationic polymerization of VCZ is induced by some donor-acceptor type interaction between VCZ and CAL.
  • Ichiro Takemura, Hiroshi Sumitomo
    1969 Volume 42 Issue 3 Pages 634-636
    Published: 1969
    Released: March 27, 2006
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    Radical initiated copolymerization of β-cyanoacrolein (CAL, M2) with acrylonitrile (M1) in benzene at 60°C was investigated. The monomer reactivity ratios were determined to be r1=3.2 and r2=0. The copolymerization behavior is discussed in comparison with that in the system of styrene and CAL previously described. The Q and e values of CAL were also estimated to be 0.53 and 2.07, respectively, which were compared with those of other polar monomers.
  • Yôichi Iida
    1969 Volume 42 Issue 3 Pages 637-643
    Published: 1969
    Released: March 27, 2006
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    The present paper deals with crystalline TCNQ anion radical “complex” salts of (M+)2-(TCNQ)3\ ewdot\ ewdot and M+(TCNQ)2\ ewdot composed of the formally-neutral TCNQ and its anion radical TCNQ\ ewdot Their crystalline electronic spectra were measured in the range between 4.0 and 30.8 kK by diffuse reflectance and in the 0.65–4.0 kK range by transmittance. None of their spectra except those of the (2 : 3) compounds were found to bear any resemblance to those in the simple salts. Although the spectra of the (2 : 3) compounds are similar to those of the simple salts with low conductivities, the former exhibit an additional weak absorption in the range lower than 6 kK. The (1 : 2) compounds with intermediate conductivities show a strong band around 3 kK, and those with high conductivities, around 2.0–2.5 kK. Their spectra are discussed on the basis of the interaction among unpaired electrons in connection with their electrical and magnetic properties. The difference in the interaction modes of the ion radicals between “simple” and “complex” salts is also speculated upon.
  • Tetsuya Ogura, Nobuo Furuno, Shinichi Kawaguchi
    1969 Volume 42 Issue 3 Pages 643-650
    Published: 1969
    Released: March 27, 2006
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    Diallyl ether was produced exclusively when an allyl alcohol solution containing copper(I) chloride and ammonium chloride was heated in the absence of air. A mixture of allyl and ethyl alcohols gave diallyl and ethyl allyl ethers, but no trace of diethyl ether. The tracer experiment employing 18O-enriched allyl alcohol showed that the C–O bond in allyl alcohol was ruptured in the ethyl allyl ether formation. The kinetic study of these etherification reactions showed that the rate determining step would include the nucleophilic attack of an allyl or ethyl alcohol molecule on the catalyst-substrate complex. A novel allyl alcohol complex, (NH4)2Cu2Cl4(C3H6O)2, was isolated and characterized, but the active catalyst species was assumed to be (NH4)2Cu4Cl6. Methyl derivatives of allyl alcohol were also allowed to react in the presence of the same catalyst and the possible mechanism of etherification was discussed.
  • Teijiro Yonezawa, Isao Noda, Takashi Kawamura
    1969 Volume 42 Issue 3 Pages 650-657
    Published: 1969
    Released: March 27, 2006
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    Electron spin resonance (ESR) studies were made on various radicals formed from formamide, acetamide, N-methylformamide, N-methylacetamide, N,N-dimethylformamide and propionamide by hydrogen abstraction with hydroxyl radicals produced by the reaction of hydrogen peroxide and titanium trichloride in aqueous solution, using a rapid flow technique. In each case, except for formamide, various π-electron radicals were found. For formamide, N-methylformamide, and N,N-dimethylformamide, carbamoyl and its methyl substituted σ electron radicals were detected. The g factor of the σ electron radical is qualitatively discussed.
  • Akira Yokohata
    1969 Volume 42 Issue 3 Pages 658-663
    Published: 1969
    Released: March 27, 2006
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    Based on radiation chemistry of water a study on the chemical changes resulting from the silent electric discharge of aqueous solution under argon atmosphere was made for the purpose of elucidating the nature of the reducing species formed. In the neutral aqueous ClCH2COOH system the effects of such additives as CH3OH and NO3 on the yield of Cl and in the system containing NO3 the yield of NO2 were investigated. Moreover, in the alkaline aqueous K3Fe-(CN)6 system emphasis was placed on the yield of aquocomplex. In view of the non-dependence of the yield of Cl on the concentration of additive NO3 and of the low yields of NO2 and Fe(CN)5OH23− produced, it was concluded that in the silent electric discharge the yield of solvated electrons which react with solutes in the bulk of water is very small (G\lesssim0.06). Reasons for the low yield of solvated electrons are briefly described.
  • Shuji Saito
    1969 Volume 42 Issue 3 Pages 663-666
    Published: 1969
    Released: March 27, 2006
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    The microwave spectra of the normal species as well as the 13C and 34S isotopic molecules of ethylene episulfoxide have been observed. The rotational constants thus obtained lead to the following structural parameters: S–O=1.483±0.003 Å, C–S=1.822±0.003 Å, ∠OSC=111°1′±10′, ∠CSC=48°46′±10′, on the assumption that the C–H distance and the ∠HCH and ∠H2CC angles are the same as those of ethylene sulfide. From the Stark shifts, the dipole moment has been determined to be μa=3.61±0.04 D, μc=0.89±0.01 D and μtotal=3.72±0.04 D. The bond nature of S–O and C–S has then been discussed on the basis of these data.
  • Shuji Saito
    1969 Volume 42 Issue 3 Pages 667-670
    Published: 1969
    Released: March 27, 2006
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    Microwave spectroscopy has been applied to the study of the pyrolysis of ethylene episulfoxide in the vapor phase. The rotational lines of SO in the electronic ground state, 3Σ, were observed with a good signal-to-noise ratio. The pyrolyzed sample of ethylene episulfoxide was analyzed semi-quantitatively by the use of the microwave spectra. It turned out that ethylene episulfoxide really decomposed into ethylene and sulfur monoxide. The mechanism of the thermal decomposition is discussed in detail.
  • Takako Amano, Haruo Kuroda, Hideo Akamatu
    1969 Volume 42 Issue 3 Pages 671-676
    Published: 1969
    Released: March 27, 2006
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    The polarized absorption spectra in the 280–1100 mμ region have been observed for the single crystals of eight molecular compounds which involve N,N,N′,N′-tetramethylbenzidine and benzidine as the electron donor and p-chloranil, TCNQ, 1,3,5-trinitrobenzene, and p-benzoquinone as the electron acceptor. The donor and acceptor molecules are not in the ionic states in the ground states of these molecular compounds, in spite of the low ionization potentials of tetramethylbenzidine and benzidine. The observed spectra are composed of absorption bands associated with intramolecular transitions in the constituent molecules and those associated with the charge transfer from the donor to the acceptor. It was found that the polarization of the second charge transfer band is almost perpendicular to that of the first one in the case of chloranil and TCNQ, compounds of benzidine and tetramethylbenzidine. In other cases, the first and second charge transfer bands were confirmed to be polarized nearly parallel to each other as in a usual charge transfer molecular compound.
  • Takashi Maekawa, Toshio Yokokawa, Kichizo Niwa
    1969 Volume 42 Issue 3 Pages 677-681
    Published: 1969
    Released: March 27, 2006
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    The solubility of silver oxide in Na2O-B2O3 melts was determined as a function of the Na2O contents, the temperature (825°C–935°C), and the oxygen partial pressures. The results show that the silver oxide dissolves in a borate as a network modifier, just like alkali metal oxides, which destroy the B–O–B bonds to produce four coordinated boron as well as three. In the Ag2O-B2O3 binary system, the solubility of silver oxide increases with an increase in the oxygen partial pressures. In the Ag2O-Na2O-B2O3 ternary system, the solubility of Ag2O decreases with an increase in the Na2O contents. This shows that the silver oxide is a weaker base than sodium oxide. The activity of the oxygen ion, ao=, was determined from the iso-activity lines of silver oxide. In a constant basic oxide content, ao= increases with an increase in the Na2O content. By extrapolating the Ag2O contents to zero, the oxygen-ion activity in the Na2O-B2O3 melt was determined.
  • Hiroshi Kodama, Yoshihiro Kimura, Toshio Yokokawa, Kichizo Niwa
    1969 Volume 42 Issue 3 Pages 681-685
    Published: 1969
    Released: March 27, 2006
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    The electrical resistance of the Ag2O-B2O3 and Ag2O-Na2O-B2O3 systems has been measured in the approximate temperature range from 750 to 1000°C. The equivalent conductance at 900°C and the activation energy of the conductance for the Ag2O-B2O3 system were calculated. They were then compared with the corresponding values of alkali borate melts. The results led to the conclusion that the silver ion is not bound to the oxygen ion in the melt, but behaves like Li+, Na+, and K+ which are known to be monovalent network modifiers and to be free to move in the melt.
  • Tohru Azumi, Mitsuo Ito, Saburo Nagakura
    1969 Volume 42 Issue 3 Pages 685-689
    Published: 1969
    Released: March 27, 2006
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    The Zeeman splitting of pyrazine phosphorescence is observed. The amount of splitting is 1.4 cm−1 under the magnetic field of 15 kilogauss. This magnitude is just what one expects for the free spin, which means that the zero-field splitting parameters are small compared with the observed splitting. On the assumption of random orientations of the pyrazine molecules in the sample, the phosphorescence intensities from the three split subcomponents are expected to be in the ratio of 13g1 : 16g0 : 13g−1 where g’s represent populations. This expectation is roughly manifested in the experimental observation. Finally, the theoretical calculation of the zero-field splitting parameters, D and E, is attempted, and the results are interpreted in terms of the experimental data.
  • Yasuaki Shimoishi
    1969 Volume 42 Issue 3 Pages 690-693
    Published: 1969
    Released: March 27, 2006
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    2-(1,8-Dihydroxy-3,6-disulfo-2-naphthylazo)-phenoxyacetic acid reacts with the uranyl ion in an acidic medium to form a violet chelate. The composition of the chelate is 1 : 1 in the molar ratio. The apparent stability constants over the pH range from 3.4 to 5.2 and the formation constant of the chelate, are estimated spectrophotometrically at 25°C and an ionic strength of 0.1 by the use of KNO3. The value of the formation constant was calculated as 1.25×1010 from the apparent stability constants.
  • Kichinosuke Hirokawa, Hidehiro Gotô
    1969 Volume 42 Issue 3 Pages 693-695
    Published: 1969
    Released: March 27, 2006
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    A small plasma jet burner for direct excitation of metal solid samples was developed. The optimum operating conditions are as follows; d.c. arc current about 15 A, flow rate of nitrogen tangentially introduced gas about 1.5–2 l/min, and that of atomizer gas about 3.5–4 l/min. The limit of detection of some elements were determined with solution samples. Satisfactory-calibration curves were also obtained for analyses of alloying elements in some solid form alloys.
  • Takanobu Shiokawa, Takashi Omori
    1969 Volume 42 Issue 3 Pages 696-701
    Published: 1969
    Released: March 27, 2006
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    The chemical behavior of 144Pr as a result of the β-decay of the 144Ce(III)-diethylenetriaminepentaacetate (144Ce(III)-DTPA) complex was investigated in detail on the basis of the substitution reaction mechanism. The experimental results, represented in terms of the yield of the 144Pr(III)-DTPA complex, were explained quantitatively by the application of Bateman’s equation. An increase in the nuclear charge in the β-decay of the 144Ce(III)-DTPA complex may result in the formation of 144Pr(IV)-DTPA, which would then be reduced to an intermediate complex of 144Pr(III) by an intramolecular electron-transfer. The mechanisms and the rate constants are established for the decomposition of the intermediate leading to the formation of the uncomplexed ion. It was also suggested that the uncomplexed 144Pr(III) ion is produced directly by an exhaustive bond-rupture of the daughter complex ion, without any formation of the intermediate. The ratio of bond-rupture was determined to be 0.25; this value is in accordance with the theoretical value for the formation of the multiply-charged 144Pr ion due to electron shake-off and the internal conversion of γ-rays, followed by the Auger process.
  • Tasuku Ito, Nobuyuki Tanaka, Ichiro Hanazaki, Saburo Nagakura
    1969 Volume 42 Issue 3 Pages 702-709
    Published: 1969
    Released: March 27, 2006
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    The SGF MO’s for the π-electron system of 1,10-phenanthroline have been determined by following the Pariser-Parr-Pople’s treatment. For the description of the lower excited states, the configuration interaction among nineteen singly-excited configurations with lower energy has been taken into account. The electronic spectrum of 1,10-phenanthroline has been interpreted on the basis of the results of the theoretical calculation. The SCF MO’s for the π-electron system of a coordinated 1,10-phenanthroline in the tris-iron(II) complex have been determined to be self-consistent under the electrostatic potential field of the central metal ion and the other ligand molecules. On the basis of the results for coordinated ligand, the π-electronic structure of tris-(1,10-phenanthroline)iron(II) ion has been investigated from the theoretical point of view. It has been shown that two kinds of the charge-transfer transitions are responsible for an intense absorption band in the visible region, namely electron transfers from the 3dπ orbital of iron to the lowest and the second lowest vacant π MO’s of the ligand 1,10-phenanthroline. The discussions have been given on the change of the π–π* states of 1,10-phenanthroline by the coordination.
  • Hanako Kobayashi, Ikuji Tsujikawa, Masayasu Mori, Yoshihisa Yamamoto
    1969 Volume 42 Issue 3 Pages 709-715
    Published: 1969
    Released: March 27, 2006
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    Nitrosylpentaamminechromium chloride (brown), perchlorate (green) and other salts of different colors were studied by visible, IR and ESR spectroscopy and by magnetic susceptibility measurements. The easy shift of visible absorption bands caused by the replacement of outer anions which are responsible for the color difference, ripples observed in one of the absorption bands, g-values from ESR and a spin state 1/2 suggested by the susceptibility measurements are interpreted on the basis of a qualitative MO theory for metal nitrosyl complexes.
  • Takeshi Sotobayashi, Toshio Suzuki, Seitaro Koyama
    1969 Volume 42 Issue 3 Pages 716-720
    Published: 1969
    Released: March 27, 2006
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    The atmospheric fractionation of induced radionuclides is discussed in some detail on the basis of results obtained by making a radiochemical analysis of fresh nuclear debris originating from recent Chinese nuclear test explosions. Among fresh nuclear debris particles collected at Niigata about 4000km downwind from the Chinese test site, the trend for the enrichment of 239Np was somewhat modified as compared with that derived from an averaged sample collected by a large-scale and high-altitude sampling procedure; more 239Np was present in smaller-size fallout particles. Furthermore, it was found, in rain-water samples collected after the third Chinese nuclear explosion, that the atomic ratio at time-zero of 60Co/95Zr increased with a decrease in the 95Zr-concentration in rain and vice versa. This suggests that the atmospheric fractionation of 60Co-rich particles from 95Zr-rich ones takes place during the travel of atomic clouds around the world.
  • Mutsuo Kodama, Yayoe Tominaga
    1969 Volume 42 Issue 3 Pages 721-724
    Published: 1969
    Released: March 27, 2006
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    D.c. polarographic behavior of thallium(I) ion in 2,2′-ethylenedioxybis[ethyliminodi(acetate)] (GEDTA) and cyclohexane-1,2-diamine-N,N,N′,N′-tetraacetate (CyDTA) solutions was studied systematically. Compositions and stability constants of thallium(I)-GEDTA and CyDTA chelates were determined from the shift of the half-wave potential. In both GEDTA and CyDTA systems, thallium(I) ion gave a single well-defined wave corresponding to the following reversible one electron reduction.
    (Remark: Graphics omitted.)
    In contrast to the finding of Anderegg and Bottari, thallium(I) ion was found to form not only a normal chelate but also a protonated chelate with CyDTA.
  • Mutsuo Kodama, Yayoe Tominaga
    1969 Volume 42 Issue 3 Pages 724-727
    Published: 1969
    Released: March 27, 2006
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    D. c. polarographic behavior of copper(II) in ethylenediamine-N,N,N′,N′-tetrapropionate (EDTP) and diethylenetriaminepentaacetate (DTPA) solutions was studied systematically. In EDTP solution, copper(II) ion invariably gave a single well-defined wave corresponding to the following reduction.
    CuX2−+nH++Hg+2e=Cu(Hg)+HnXn−4
    In the DTPA solution, copper(II) ion gave a single wave reversible in nature at pH below 5.0, corresponding to the following electrode reaction.
    (Remark: Graphics omitted.)
    At higher pH, however, two waves could be observed. The second step was irreversible and its wave-height increased with increasing pH at the expense of the height of the first step.
  • Yoshiaki Ohgo, Juji Yoshimura, Tetsuo Sato
    1969 Volume 42 Issue 3 Pages 728-731
    Published: 1969
    Released: March 27, 2006
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    Stereoselectivity of the organomagnesium reaction with N-benzyl-2,3-O-isopropylidene-D-glyceraldimine was examined under various conditions (change of molarity, solvent, and composition ratio of reagents). The selectivity was not effected by the molarity of the reagents but by the solvent. When the substrate was treated with a mixture of various ratio of magnesium bromide and diphenylmagnesium, a remarkable effect of the ratio on the stereoselectivity was observed. Maximum ratio of erythro/threo was obtained at the point of equimolar mixture of magnesium bromide and diphenylmagnesium in ether. The structure of the transition intermediate was discussed.
  • Yoshio Otsuji, Hideo Yabune, Eiji Imoto
    1969 Volume 42 Issue 3 Pages 732-737
    Published: 1969
    Released: March 27, 2006
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    The treatment of dimethyl 3-nitrophthalate (I) with a mixture of dimethyl sulfoxide and sodium methoxide, followed by the acidification of the resulting mixture with hydrochloric acid, gave azoxybenzene-2,2′,3,3′-tetracarboxylic acid (II) and 3-nitrophthalic acid (III). The similar treatment of dimethyl 4-nitrophthalate (IV) afforded 5-methoxy-2-nitroso-1,3-indanedione (V) and 4-methoxyphthalic acid (VI). The similar treatment of dimethyl 4-methoxyphthalate (XV) and dimethyl phthalate gave 2-chloro-2-methylthio-5-methoxy-1,3-indanedione (XVII) and 2-chloro-2-methylthio-1,3-indanedione (XIX) respectively. The general features of these reactions are described.
  • Tadashi Suehiro, Koji Eimura
    1969 Volume 42 Issue 3 Pages 737-740
    Published: 1969
    Released: March 27, 2006
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    Bei der Einwirkung von Acetanhydrid-Schwefelsäure auf 5-Oxo-2-methyl-4,4-dibenzyl-3-äthoxycarbonyl-4,5-dihydro-indol (I) bei 0°C, findet eine Dienon-Phenol-Umlagerung von I zu 4-Acetoxy-2-methyl-5,6-dibenzyl-3-äthoxycarbonyl-indol (III) statt, dessen Struktur aus der leichten Verseifbarkeit der 3-Äthoxycarbonyl-Gruppe von III und aus den spektroskopischen Befunden der von III abgeleiteten Verbindungen folgte.
  • Yoshio Iwakura, Keikichi Uno, Nobuo Nakabayashi, Wen-Yen Chiang
    1969 Volume 42 Issue 3 Pages 741-745
    Published: 1969
    Released: March 27, 2006
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    Vinyl sulfonyl (β-chloroethyl)amide (III) was prepared from vinyl sulfonyl chloride and aziridine. The monomer reactivity ratios of III (M2) (r1=3.0, r2=0.075) were determined from the result of copolymerization with styrene (M1), and Q2 and e2 values calculated were 0.13 and 0.42 respectively. Radical polymerization of III gave a polymer with low viscosity and the polymer had good reactivity with nucleophilic reagents. To compare the functional group in polymer chain with that of monomeric compound, methane sulfonyl (β-chloroethyl)amide (IV) was prepared and the reaction between the function and several nucleophiles was studied. Reactive fibers were obtained from copolymers of acrylonitrile and III. Reaction of the fibers with Congo Red was carried out in the presence of pyridine.
  • Sotaro Miyano, Mitsuhiko Hida, Harukichi Hashimoto
    1969 Volume 42 Issue 3 Pages 746-749
    Published: 1969
    Released: March 27, 2006
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    Styrene oxide was deoxygenated to styrene in 83% yield by zinc metal and zinc chloride in aqueous ether. Under the same reaction conditions phenyl glycidyl ether gave only 2.8% of phenyl allyl ether, and propylene oxide did not give propylene. Effects of the reaction variables on the deoxygenation of styrene oxide were investigated. The yield of styrene was varied with metal halide in anhydrous THF in the following order; ZnI2>ZnCl2∼ZnBr2>AlCl3>SnCl4>FeCl3>NaI>>MgBr2. Styrene was formed from styrene oxide by zinc metal and zinc chloride in ca. 50% yield in THF, acetone, acetic acid, and aqueous ethanol, but not in anhydrous benzene. The yield of styrene increased almost proportionally with the increase of the molar ratio of zinc chloride to styrene oxide up to 1:1. 2-Phenyl-2-chloroethanol gave styrene when treated with zinc metal in the presence or absence of zinc chloride, but 1-phenyl-2-chloroethanol did not. Possible reaction paths of the deoxygenation of styrene oxide by zinc metal and metal halide were discussed.
  • Hideaki Kawashima, Izumi Kumashiro
    1969 Volume 42 Issue 3 Pages 750-755
    Published: 1969
    Released: March 27, 2006
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    6-Methoxy- and 6-ethoxypurine 3-N-oxides were obtained by the direct oxidation of the corresponding 6-alkoxypurines with hydrogen peroxide in aqueous acetic acid. 6-Chloropurine was oxidized with monoperphthalic acid in ether to give 6-chloropurine 3-N-oxide. These purine 3-N-oxides were then converted to hypoxanthine 3-N-oxide by hydrolysis with a sodium hydroxide solution. 6-Methoxypurine 3-N-oxide and hypoxanthine 3-N-oxide were identified with authentic samples unambiguously synthesized from 6-methylsulfonylpurine 3-N-oxide, which had itself been obtained by the oxidation of 6-methylthiopurine 3-N-oxide. The treatment of hypoxanthine 3-N-oxide with hydrochloric acid gave 6,8-dihydroxypurine, 8-chlorohypoxanthine, hypoxanthine, and 2-chloro-4-amino-5-imidazolecarboxamide.
  • Akihisa Sakumoto
    1969 Volume 42 Issue 3 Pages 755-760
    Published: 1969
    Released: March 27, 2006
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    Ammonia and aqueous ammonia solutions of benzoic acid, 14C-carboxyl labeled, were irradiated with 60Co γ-rays at absorbed doses of 1.9×1020 and 4.4×1020eV/g respectively. The irradiation temperature was 0°C in both cases. An isotope dilution method was applied to measure the products in irradiated solutions. The G values of o-, m-, and p-aminobenzoic acids were 0.016, 0.022, and 0.027 respectively in an ammonia solution. On the other hand, the G values of products in an aqueous ammonia solution were 0.011, 0.013, and 0.017 for o-, m-, and p-aminobenzoic acids and 0.029, 0.033, and 0.040 for o-, m-, and p-hydroxybenzoic acids. The disappearance of benzoic acid in an ammonia solution corresponded to a G value of about 1.46. From the ratio of the relative partial rate factors, it was deduced that the aminating agent was the amino radical in both cases.
  • Yoshio Okamoto, Masahiko Kato, Heimei Yuki
    1969 Volume 42 Issue 3 Pages 760-765
    Published: 1969
    Released: March 27, 2006
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    The reaction of trans-stilbene with n-butyllithium was investigated in tetrahydrofuran at 0°C. The structures of the products fractionated by column chromatography were determined by elementary analysis, a molecular-weight determination, and a study of the IR, UV, and NMR spectra. The main products were 1,2-diphenylhexane, 1,2-diphenylethane, and 1,2,3-triphenyl-propene which was formed by the cleavage of a C–C bond of a product. The reaction mixture showed an ESR signal. The observed results are explained in terms of the anionic copolymerization of trans-stilbene and styrene reported previously.
  • Takeo Sato, Shigeru Shimada, Kazuo Hata
    1969 Volume 42 Issue 3 Pages 766-772
    Published: 1969
    Released: March 27, 2006
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    Electronic effects on the photochemical conversion of o-terphenyl to triphenylene were examined by comparing the ultraviolet irraiation reaction, carried out in a benzene solution using iodine as an oxidant, of three classes of o-terphenyl derivatives, 4- (3) and 4′-substituted (4) and 4,4″-disubstituted derivatives (5). While a strong electron-withdrawing group such as nitro group, hindered the cyclization reaction to occur, methoxy, fluoro, chloro and bromo compounds afforded the corresponding triphenylene derivatives. With bromo and iodo compounds, however, a complex mixture of the products resulted due to photochemical cleavage of a carbon-halogen bonding, which led to the formation of phenylation products and hence phenyltriphenylenes together with reduction products. Further, with iodo compounds, it was found that no oxidant was necessary to effect the cyclodehydrogenation reaction since iodine was liberated during the photolysis. Possible pathways for the formation of the photolysis products from bromo and iodo compounds were discussed in relation to the relative rates of carbon-halogen cleavage and cyclization reactions. Comparison among three classes of halogeno compounds indicated that, with the exception of iodides, the cyclization reaction occurred more readily with type 4 compound than type 3 compounds, while type 5 compounds reacted only with difficulty.
  • Takeo Sato, Meiko Wakabayashi, Shigenari Hayashi, Kazuo Hata
    1969 Volume 42 Issue 3 Pages 773-776
    Published: 1969
    Released: March 27, 2006
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    The ultraviolet irradiation of [2.2]metacyclophane (I) with iodine in a cyclohexane solution was shown to afford 4,5,9,10-tetrahydropyrene (II), which, on further dehydrogenation, was led to 4,5-dihydropyrene and pyrene. The transannular reaction leading to II occurred much more rapidly than the subsequent dehydrogenation reactions. Thus II was obtainable in an optimum yield of 62% by the irradiation of I in the presence of an equimolar amount of iodine and an excess of sodium bicarbonate. By ESR and UV spectral studies, 253.7 mμ light was found to be responsible for the transannular reaction.
  • Yoichi Mori, Jiro Tsuji
    1969 Volume 42 Issue 3 Pages 777-779
    Published: 1969
    Released: March 27, 2006
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    It was found that the carbonylation of β-propiolactone can be carried out in the presence of dicobalt octacarbonyl. Butyrolactone and succinic acid were obtained by the reaction of β-propiolactone with carbon monoxide and hydrogen. Succinic anhydride was obtained by the reaction with carbon monoxide.
  • Hiroshi Minato, Nobuyuki Higosaki, Chieko Isobe
    1969 Volume 42 Issue 3 Pages 779-781
    Published: 1969
    Released: March 27, 2006
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    Naphthalene was polymerized by use of anhydrous aluminum chloride. The polynaphthalene formed was soluble in various organic solvents. The molecular weight determination suggested that the average degree of polymerization was six. The NMR spectrum indicated the presence of non-aromatic hydrogens, and the elemental analysis roughly corresponded with (C10H8)n. The reactions of the polymer was examined such as hydrogenation, bromination, thermal dehydrogenation, chloromethylation and epoxidation.
  • Haruhiko Aoyagi, Tetsuo Kato, Michinori Waki, Okitoshi Abe, Reiko Okaw ...
    1969 Volume 42 Issue 3 Pages 782-789
    Published: 1969
    Released: March 27, 2006
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    Two analogs of gramicidin S, 4,4′-D-valine- and 4,4′-D-leucine-gramicidin S (XVI-A and XVI-B), have been synthesized and tested for the antibacterial properties. The crude product obtained after the cyclization of a linear pentapeptide active ester was composed of the protected monomer and dimer. The pure protected dimer was obtained by a column chromatography of Sephadex LH-20, and the hydrogenolysis of this product in the presence of hydrogen chloride afforded the crystalline hydrochloride of XVI-A or XVI-B. These analogs were as active as natural gramicidin S; the results indicated that the aromatic side chains of the D-phenylalanines in the molecule of gramicidin S can be replaced by the aliphatic side chains without an influence for the activity.
  • Sumio Chubachi, Hideo Matsui, Kiyoshi Yamamoto, Sachio Ishimoto
    1969 Volume 42 Issue 3 Pages 789-794
    Published: 1969
    Released: March 27, 2006
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    One of the major reaction products besides cyclohexanol from the reaction of cyclohexyl hydro-peroxide with cyclohexanone was isolated and confirmed as ε-cyclohexyloxycaproic acid. The rate of formation of ε-cyclohexyloxycaproic acid was measured in excess cyclohexanone and found to follow a first order law for cyclohexyl hydroperoxide. The activation energy of 10.1 kcal/mol was found for the formation of the acid. The rate of decomposition of cyclohexyl hydroperoxide in cyclohexane was measured in the presence of various concentrations of cyclohexanone and the rates of formation of cyclohexanol and the free carboxylic acids were also measured. An adduct formation between cyclohexyl hydroperoxide and cyclohexanone followed by homolytic decomposition of the adduct was suggested to explain the experimental results.
  • Yoshiro Ogata, Teruo Itoh, Yasuji Izawa
    1969 Volume 42 Issue 3 Pages 794-797
    Published: 1969
    Released: March 27, 2006
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    The ultraviolet light-induced reaction of ethyl haloacetate with an excess benzene gives ethyl phenylacetate (1.7%) and diethyl succinate (1.6%) as main products, while the same reaction of excess chloroacetate with benzene gives ethyl phenylacetate higher yield (optimum 78.4%). Addition of aluminum chloride to the reaction mixture using an excess benzene gives ethyl phenylacetate as a sole product (11.5%). The effect of reaction conditions on the yield is examined.
  • Mikio Shiga, Hiromichi Kono, Izumi Motoyama, Kazuo Hata
    1969 Volume 42 Issue 3 Pages 798-801
    Published: 1969
    Released: March 27, 2006
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    The condensation reactions of β-ferrocenylnitroethylene (1), with various aromatic aldehydes in the presence of an excess of sodium methoxide were investigated. The main products of these reactions were ferrocenylnitroalkenols (2), which were obtained from precursory sodium salts by the acidification of the reaction mixture. Sodium nitroalkanolate (4) was postulated as an intermediate in these reactions. On the other hand, the reaction of 1 with acetophenone resulted in a different condensation, one giving 1-benzoyl-2-ferrocenyl-3-nitropropane (11) and 1-benzoyl-2-ferrocenylethylene (12).
  • Yasuhide Yukawa, Toshikazu Ibata
    1969 Volume 42 Issue 3 Pages 802-805
    Published: 1969
    Released: March 27, 2006
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    Kinetic isotope effect of the Wolff rearrangement of carbonyl-14C and phenyl-1-14C labeled α-diazoacetophenone was measured in t-butyl alcohol at 30°C, using a solution of silver benzoate in triethylamine as a catalyst. No apparent kinetic isotope effect was observed in both cases within experimental error. These results suggest that the elimination of nitrogen and the migration of phenyl group proceed in two steps in the rate-determining step.
  • Sinzo Imamura, Tsunesuke Kajimoto, Yukishige Kitano, Jiro Tsuji
    1969 Volume 42 Issue 3 Pages 805-808
    Published: 1969
    Released: March 27, 2006
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    Ligand exchange reactions of palladium complexes having π-allyl and acetylacetonate as ligands with cyclohexanone oxime were carried out and the formation of several new oxime complexes was reported.
  • Shumpei Sakakibara, Ichiro Honda, Katsumi Takada, Muneji Miyoshi, Taka ...
    1969 Volume 42 Issue 3 Pages 809-811
    Published: 1969
    Released: March 27, 2006
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    t-Amyloxycarbonylamino acids (Aoc-amino acids) were found to be synthesizable under the conditions of the Schotten-Baumann reaction with t-amyl chloroformate in the presence of a water-soluble inert solvent. The procedure was applied to almost all amino acids or their derivatives; the yields of the products and their purities were satisfactory except in the cases of asparagine, glutamine, and nitroarginine. Many t-butyloxycarbonylamino acids (Boc-amino acids) were also synthesized successfully using the same procedure. Similarly, t-amyl and t-butyl carbazates were synthesized in satisfactory yields with these chloroformates and hydrazine hydrate. Thus, the procedure was demonstrated to be the simplest for the preparation of Aoc-or Boc-amino acids and hydrazide.
  • Shoichi Kusumoto, Tomomi Okazaki, Akio Ohsuka, Munio Kotake
    1969 Volume 42 Issue 3 Pages 812-820
    Published: 1969
    Released: March 27, 2006
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    A new bitter principle, solidagonic acid C22H34O4, was isolated from the root of Solidago altissima L. It is a bicyclic diterpene carboxylic acid, having an acetoxyl group and two double bonds, and was formulated as II on the basis of chemical and spectroscopic studies. The other constituents of the root, kolavenic acid (XXIV) and kolavenol (XXVIII) were also isolated, and they were chemically correlated to II. The absolute configurations of II, XXIV and XXVIII were established by application of the octant rule on the ORD curves for some ketonic compounds derived from them.
  • Ken-ichi Terauchi, Hiroshi Sakurai
    1969 Volume 42 Issue 3 Pages 821-823
    Published: 1969
    Released: March 27, 2006
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  • Ko Taki, Pil Hyon Kim, Susumu Namba
    1969 Volume 42 Issue 3 Pages 823-825
    Published: 1969
    Released: March 27, 2006
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  • Tadashi Sasaki, Toshiyuki Yoshioka
    1969 Volume 42 Issue 3 Pages 826-827
    Published: 1969
    Released: March 27, 2006
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