Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 40 , Issue 1
Showing 1-50 articles out of 63 articles from the selected issue
  • Kazuo Nakamura
    1967 Volume 40 Issue 1 Pages 1-7
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The ESR spectra of the ion-pair complexes of the m-iodonitrobenzene anion with alkali and alkaline earth cations were measured. Cation-induced variations in the nitrogen and proton splitting constants were found. When the observed alkali metal splittings were related to the back-transferred charge, ρ, on the ns-shell of each metal, ρ increased in the sequence: Li<Na<K<Rb<Cs at 20°C. The solvent and the temperature effects on alkali-metal splitting varied with the alkali metal. The Cs and Rb splitting constants increased in the sequence: DME<THF<THP solutions, and were independent of the temperature. The Na and Li splitting constants decreased in the above sequence of solvents. With a lowering of the temperature, the Na splitting constant decreased while the Li splitting constant increased. The K splitting constant was independent of both the temperature and the solvent. These results were found in the ion pairs of other halogeno-nitrobenzenes, also.
  • Hiroshi Takahashi, Kazuo Tsutsumi
    1967 Volume 40 Issue 1 Pages 7-11
    Published: 1967
    Released: March 27, 2006
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    The structural change in zinc oxide by mechanical treatment was studied. In the process of the mechanical treatment of zinc oxide, the crystallite size and the lattice distortion as measured by the X-ray diffraction method, the specific surface area as measured by the BET method, and the density as measured by a pycnometer changed monotonously with the treatment time. Such monotonous changes correspond to a primary structural change in zinc oxide.
  • Akihiro Kagemoto, Sachio Murakami, Ryoichi Fujishiro
    1967 Volume 40 Issue 1 Pages 11-15
    Published: 1967
    Released: March 27, 2006
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    In order to ascertain the dependence of the interaction parameter, χH, between the polymer and the solvent molecules on the polymer concentration, the heats of dilution in an atactic polymethyl methacrylate solution have been measured for the polymers with the degrees of polymerization of 3000 and 7800. It was found that the values of χH obtained are dependent on the concentration in all the solvents used, as in the solutions of polystyrene and polybutadiene reported as in previous papers. χH depends also on the molecular weight, this is in agreement with the suggestion by Huggins (J. Am. Chem. Soc., 86, 3535 (1964)).
  • M. Arshad, A. Beg
    1967 Volume 40 Issue 1 Pages 15-18
    Published: 1967
    Released: March 27, 2006
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    The boiling point and density of the phosphines have been correlated by using the quantity Mρ2. The use of such data permits the classification of these compounds into associated and normal liquids. These conclusions are also supported by the study of the heat of evaporation of the phosphines.
  • N. K. Mehrotra, M. C. Saxena
    1967 Volume 40 Issue 1 Pages 19-20
    Published: 1967
    Released: March 27, 2006
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    The relaxation times of 2-chloro-, 2-bromo-, 3-bromo-, 2-methyl-, 2-acetyl- and 2-hydroxy-pyridines have been determined in the 3 cm microwave region at 20°C using benzene as solvent. It has been concluded from the relaxation times of 2-chloro-, 2-bromo-, 3-bromo- and 2-methylpyridines that these rigid molecules relax predominantly by the process of over-all molecular rotation. The comparatively small relaxation times of 2-acetyl- and 2-hydroxypyridines suggest that these non-rigid molecules relax by both molecular as well as intramolecular rotations. The free energies of activation for dipole orientation for the compounds investigated are always found to be smaller than those for viscous flow, because the process of dipole orientation involves only rotation, while the process of viscous flow involves both rotation and translation.
  • Akira Imamura, Hiroko Fujita, Chikayoshi Nagata
    1967 Volume 40 Issue 1 Pages 21-27
    Published: 1967
    Released: March 27, 2006
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    The electronic structures of β-naphthol, the base components of nucleic acids, and peptide have been calculated for the ground, singlet-excited, and triplet-excited states by means of the ASMO SCF CI method. The calculated π electron density of β-naphthol agrees well with the experimental data. The π electron density, the dipole moment, and the bond order for the ground, singlet and triplet excited states have been obtained, and the characteristics of the electronic structures for the ground, singlet-excited, and triplet-excited states have been discussed in connection with the chemical behavior of the molecule.
  • Tatsuya Sekine, Muneo Isayama, Sumiko Yamaguchi, Hiromitu Moriya
    1967 Volume 40 Issue 1 Pages 27-32
    Published: 1967
    Released: March 27, 2006
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    The distribution of acetic, propionic and butyric acids, or of mixtures of two of these acids, between carbon tetrachloride and aqueous solutions has been studied at 25°C. The distribution data have been explained in terms of the partition of the acid monomer molecules and the dimerization of the monomer molecules in the organic phase. A salting-out effect has been observed upon additions of sodium perchlorate to the aqueous phase; this salting-out effect is larger in the order butyric>propionic>acetic acid. From the distribution data, the equilibrium constants for the distribution and the dimerization have been determined, and the formation constants for the mixed-dimer molecules have been compared with the statistical values. It has been concluded that the mixed-dimer molecules are equally stable or only a little less stable than had been statistically expected.
  • Setsuo Kashino, Norio Nishimura, Kohei Ino, Shigeo Hasegawa
    1967 Volume 40 Issue 1 Pages 33-37
    Published: 1967
    Released: March 27, 2006
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    The reaction of benzoyl peroxide with 5, 5′-indigo-disulfonic acid was studied in ethanol. The effect of the p,p′-substituents of benzoyl peroxide on the reaction rate was investigated. It was found that the reaction is a bimolecular process. Either electron-attracting substituents or electron-releasing substituents promote the reaction. This was interpreted by means of the multicenter mechanism. The electron absorption spectra of the reaction mixture showed the formation of a reasonably stable complex in ethanol. This complex is decomposed by water to 5-isatinsulfonic acid and 5, 5′-indigo-disulfonic acid.
  • Kunio Tamaki
    1967 Volume 40 Issue 1 Pages 38-41
    Published: 1967
    Released: March 27, 2006
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    The surface activity of the tetrabutylammonium halides at the air/aqueous solution interface or at the hexane/aqueous solution interface has been studied. The surface or inter facial tension versus the concentration curves of the electrolytes are markedly dependent on the kind of their counter-ions, just as with these electrolytes in aqueous solutions. The surface activity of tetrabutylammonium iodide is fairly strong; it approximately corresponds to that of the surface-active straight-chain electrolyte with an octyl group. From the thermodynamic parameters of the adsorption of tetrabutylammonium iodide, it is found that the standard free energy of adsorption becomes negative as a result of the large positive values of the standard entropy of adsorption, irrespective of the positive values of the standard enthalpy change. This suggests that the adsorption is a “hydrophobic” effect; that is, the “icebergs” around the nonpolar groups of the electrolyte return to the original water by the process of the transfer of the hydrophobic ions from the aqueous solution to the surface phase.
  • Makoto Misono, Yukio Yoneda
    1967 Volume 40 Issue 1 Pages 42-49
    Published: 1967
    Released: March 27, 2006
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    The reaction activities and the reaction products of the oligomerization of propylene on several acidic solid catalysts, e. g., silica-alumina, sodium-exchanged silica-alumina and some other acidic catalysts, have been investigated in a circulation system in the range of 130–300°C and 100–600 mmHg. The acid strength and the acid contents of catalysts were qualitatively measured by amine titration, using several indicators, over the range from 1.5 to −12.8 in H0 function. Correlations between the reaction activity of the oligomerization of propylene and the acid strength as well as the acid content of the catalysts were demonstrated. The activation energies, the pressure dependency of the rate, and the reaction products were correlated with the acid strength as well. The high activity of some catalysts due to very strong acid sites was deactivated by coke formation in the initial stage of the reaction process. On the basis of an analysis of the reaction products, the major reaction at the stationary stage was ascertained to be the trimerization of propylene, which seemed to occur on moderately strong acid sites. The acid types responsible for the activity were discussed by the aid of “added back water.”
  • Hideaki Chihara, Nobuo Nakamura, Syûzô Seki
    1967 Volume 40 Issue 1 Pages 50-58
    Published: 1967
    Released: March 27, 2006
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    The 35Cl quadrupole resonance (NQR) spectra in both the molecular (PCl5) and the ionic (PCl4+·PCl6-) solid modifications were measured and assigned, and their temperature dependences (20 to 250°K) were interpreted by a modified Bayer theory. A phase transition of higher order occurs in the ionic solid at 102.3°K which was also revealed by a preliminary heat capacity measurement: There are seven resonance lines below 102.3°K and four above it. An anisotropy in the librational motion is suggested. The molecular solid modification is metastable and transformation into the ionic solid occurs over a range of temperature. This was observed both in the quadrupole resonance spectrum and in the differential thermal analysis; the latter was used to derive the apparent activation energy for the disproportionation reaction. A phase transition occurs also in the molecular solid at 183°K. The partial ionic character of the P-Cl bonds in the two modifications was estimated from the NQR results and could account for the observed chemical shift in the nuclear magnetic resonance of 31P. The 35Cl resonance frequencies in a family of compounds PXn were correlated.
  • Toyosaburo Takeuchi, Daisaku Miyatani
    1967 Volume 40 Issue 1 Pages 58-62
    Published: 1967
    Released: March 27, 2006
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    The correlation between the bond strength of adsorbed hydrogen and the reactivity of the hydrogen toward ethylene has been investigated by using tritium as a tracer. Hydrogen (or tritium) was adsorbed first on powdered nickel at −78°C; tritium (or hydrogen) was subsequently adsorbed, and then ethylene was added. The total coverage of hydrogen in every experiment was 0.16 or 0.4 for the nickel reduced at 200°C, and 0.06 or 0.4 for the nickel reduced at 400°C. After a certain time, the hydrogen and the mixture of ethane and ethylene were drawn off successively from the reaction vessel and separated. An assay of the tritium in each fraction of the gas was then made. The results on the nickel reduced at 200°C indicate that neither the very-strongly-adsorbed hydrogen nor the weakly-adsorbed hydrogen reacts with ethylene. The results on the nickel reduced at 400°C indicate that the weakly-adsorbed hydrogen does not react with ethylene either. These findings suggest that the very strong sites for the adsorption of hydrogen, which are inactive in the hydrogenation, are diminished by the elevation of the reduction temperature.
  • Nobuko Kataoka, Akira Imamura, Yutaka Kawazoe, Goro Chihara, Chikayosh ...
    1967 Volume 40 Issue 1 Pages 62-68
    Published: 1967
    Released: March 27, 2006
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    A potent carcinogen, 4-hydroxyaminoquinoline 1-oxide, was found to produce a stable free radical oxidatively. The structure of the free radical produced in dioxane was studied by analyizng the hyperfine structure of isotope-substituted 4-hydroxyaminoquinoline 1-oxides, and by comparing the values of the spin densities obtained from the coupling constants with those calculated by the unrestricted SCF MO method. It was concluded that the free radical has the same molecular skeleton as the parent compound, but that it loses a hydrogen atom on the nitrogen atom of the NHOH group.
  • Isao Kusunoki
    1967 Volume 40 Issue 1 Pages 69-75
    Published: 1967
    Released: March 27, 2006
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    Total cross sections for the scattering of potassium by He, Ne, Ar, Kr, and Xe have been measured in the thermal energy range. The potassium beam and the scattering gases had Maxwellian velocity distributions. The angular resolution of the apparatus was 2.62 min of arc, so that quantum mechanical calculations could be applied. If a van der Waals potential, V=−Cr6, is assumed for the long range intermolecular forces, the total cross section may be related to the constant, C, as follows;(Remark: Graphics omitted.), where p is a constant. In the present experiments care was taken to avoid the pumping effect of a McLeod gauge in the measurement of the pressure in the scattering chamber. The Ga0 function denned by Berkling et al. was used to derive an absolute total cross section from a measured effective total cross section. The van der Waals constants calculated from the measured total cross sections were compared with the theoretical values. The present values were about 25 percent smaller than the theoretical values for the Ar, Kr, and Xe systems. The differences for the He and Ne were considerably larger, with the theoretical values larger than the experimental by a factor of two or three.
  • Shin-ichi Sasaki, Yasuhiro Itagaki, Tadashi Kurokawa, Koji Nakanishi, ...
    1967 Volume 40 Issue 1 Pages 76-80
    Published: 1967
    Released: March 27, 2006
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    The mass spectra of fifteen metal acetylacetonates measured under the electron impact with 70 eV energies are reported. The acetylacetonates can be divided into three groups, A, B, and C, according to their stability in mass spectrometeric measurements. When the electronegativity of the central metal atom is 1.5—1.6, the complexes show abundant molecular ion peaks (group A); when the electronegativity is 1.6—1.8, no molecular ion appears and the M-L cations show as the highest mass (group B); when the electronegativity is greater than 1.8, there are no peaks arising from fragments containing the metal, only acetylacetone peaks being apparent (group C). Furthermore, the mass spectra of hexafluoroacetylacetone and its copper complex were also measured.
  • Naomi Imai, Osamu Toyama
    1967 Volume 40 Issue 1 Pages 81-84
    Published: 1967
    Released: March 27, 2006
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    The catalytic effect of hydrogen bromide on the thermal decomposition of acetaldehyde has been studied over the temperature range from 326 to 365°C. The experimental results are similar to those previously obtained for the hydrogen chloride catalysis: the reaction is 3/2 order in the aldehyde and is independent of the hydrogen bromide pressure when the [HBr]/[CH3CHO] ratio is sufficiently high. The most probable reaction scheme to explain this order is: CH3CHO+M→CH3+CHO+M(1), CHO→CO+H(2), H+HBr→H2+Br(3), CH3+HBr→CH4+Br(4), Br+CH3CHO→HBr+CH3CO(5), CH3CO→CH3+CO(6), and Br+Br+M→Br2+M(7). The overall rate resulting from this scheme is k11⁄2k5k7−1⁄2[CH3CHO]3⁄2; the application of this rate equation to the experimental results leads to the Arrhenius expression k11⁄2k5k71⁄2=1014.65 exp-(−44000⁄RT)mole1⁄2cc1⁄2sec−1, which is consistent with the expression for k1 reported previously and with those for k5 and k7 estimated from the literature. The catalytic efficiency of hydrogen bromide is greater than that of hydrogen chloride by a factor of about forty.
  • Hiroatsu Matsuura, Tatsuo Miyazawa
    1967 Volume 40 Issue 1 Pages 85-94
    Published: 1967
    Released: March 27, 2006
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    The infrared spectra of ethylene glycol and ethylene glycol-d2 have been measured in the liquid and crystalline states in the region 4000—300 cm−1. The infrared and Raman spectra suggest that ethylene glycol molecule takes only the gauche conformation as to the C-C bond in both states (the likely models are TGT, TGG and GGG). To establish the vibrationarassignments, the normal coordinate treatments of ethylene glycol and its three deuterated derivatives have been carried out for these models by the use of GF matrix method. The modified Urey-Bradley force field has been used and the force constants have been transferred from similar molecules. The potential energy distributions have also been calculated and the nature of the observed infrared bands and Raman lines in the liquid state has been discussed. The empirical assignments of the methylene rocking modes by the previous investigators have been revised by the present normal coordinate analyses.
  • Yukio Kurita
    1967 Volume 40 Issue 1 Pages 94-96
    Published: 1967
    Released: March 27, 2006
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    The ESR of X-irradiated single crystals of 3, 3′-dithiodipropionic acid was measured at room temperature. From the analysis of the anisotropy in the spectra, the free radical produced was confirmed to be of the HO2OC·H2CH2·S form. The principal values of the g factor are 2.003, 2.025, and 2.055, while the isotropic coupling constants for the two β protons are 12.4 G and 5.3 G. In this free radical the unpaired electron is mainly concentrated in a 3pπ orbital of the sulfur atom. For the isotropic coupling constant of the β proton in this type of radical, the “Bcos2θ” rule is applied successfully using the value of 12.8 G for B.
  • Masayuki Kashiki, Kazuyoshi Ishida
    1967 Volume 40 Issue 1 Pages 97-101
    Published: 1967
    Released: March 27, 2006
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    The application of square-wave polarography to the determination of small amounts of disulfide, mercaptan and free sulfur in a mixed solution of methanol, glacial acetic acid, and sodium acetate was studied. Disulfide, mercaptan, and free sulfur in concentrations below 10 ppm were easily determined in these mixed solvents. The derivative wave heights were proportional to the concentrations predicted by the theory of s. w. polarography. The effects of changes in solvent and in supporting electrolyte concentration, dissolved oxygen, and temperature were discussed. It was determined that concentrations of 2 vol% glacial acetic acid and 1.4 M sodium acetate were necessary to obtain a constant peak height. The temperature coefficients of disulfide, mercaptan and free sulfur were about 4.5 (first wave), 0.7 and 4.5% per degree respectively in the neighborhood of 25°C. The effect of the dissolved oxygen was removed by passing nitrogen through for 5 min.
  • Junsuke Suzuki
    1967 Volume 40 Issue 1 Pages 101-104
    Published: 1967
    Released: March 27, 2006
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    The investigation of the anodic-stripping voltammetry of cadmium or thallous ions in a 0.1 M potassium nitrate solution was carried out by using the pushed-out mercury Drop Convection Electrode (cf. J. Suzuki and T. Ozaki, This Bulletin, 37, 230 (1964)). The metals were deposited on the mercury electrode by rotating the disk at 600—1200 rpm, and the stripping was performed by a linearly-varying potential method. The anodic-stripping peak current was proportional to the square roots of the rotating rate of the disk and of the voltage scanning rate, and to the bulk concentration of cadmium or thallous ions. Using the present stripping procedure, it was possible to determine thallous and cadmium ions at concentrations as low as 1×107 M with a mean error of about ±2%.
  • Shunji Utsuno, Kôzô Sone
    1967 Volume 40 Issue 1 Pages 105-109
    Published: 1967
    Released: March 27, 2006
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    Fifteen chelates of nickel and copper(II), among which twelve are new, of 6-methyl-2-aminomethylpyridine (6-methyl-2-picolylamine=“mepic”) and N-methyl-2-aminomethylpyridine (picolylmethylamine=“pma”) were prepared, and the electronic absorption spectra of their aqueous solutions were measured. The spectra observed were practically those of the chelate ions [Cu L]2+, [Cu L2]2+, [Ni L]2+, [Ni L2]2+ (L=mepic or pma) and [Ni (pma)3]2+; [Ni(mepic)3]2+ was found to be unstable in solution, and to dissociate into [Ni(mepic)2]2+ and a ligand molecule. With the exception of [Cu(pma)]2+, the wave numbers of the absorption maxima (νmax) of these chelates were all smaller than those of the corresponding 2-aminomethylpyridine (2-picolylamine=“pic”) chelates as a result of the steric hindrance caused by methyl substitution in the ligands. The nature and degree of this steric hindrance in each chelate, and the probable structure of some of these chelates, can be studied by a comparison of the obtained spectra with one another and by the use of scale models of these chelates.
  • Terumasa Nakamura, Shigeru Ohashi
    1967 Volume 40 Issue 1 Pages 110-115
    Published: 1967
    Released: March 27, 2006
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    Glasses of the NaBO2-NaPO3 system with P/B ratios in the range from 1.0 to 98.9 have been prepared from sodium metaphosphate and sodium metaborate by quenching melts of their mixtures. By the paper chromatographic analysis and the pH titration of the solutions of the glasses, it has been found that the glasses have the chain and branched structures consisting of P–O–P, P–O–B and B–O–B linkages. On the assumption that the glasses are composed of polypohsphate and polyborate chain blocks and branched BO3 units, the theoretical treatment has been made on the compositions of these blocks and units and compared with the experimental data. It has been concluded that (1) the glass with a P/B ratio of unity, i. e., a mole fraction of sodium metaphosphate m is 0.5, may be composed of chains of the P–O–P, P–O–B and B–O–B linkages, (2) with the increase of P/B ratios, the amount of the B–O–B linkages decreases, while the amount of the branched BO3 units increases and (3) in the glasses with P/B ratios larger than 4.0 (m>0.8), all boron atoms are present as the branched BO3 units.
  • Otohiko Tsuge, Masashi Tashiro
    1967 Volume 40 Issue 1 Pages 115-119
    Published: 1967
    Released: March 27, 2006
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    The reactions of DPM and its chloro derivatives with aluminum chloride in a mixture of benzene and chlorobenzene have been studied in order to obtain clearer information concerning the bond cleavage of the diarylmethanes. The constants or the activation energy of the cleavage reaction have been determined, and it has found that, in such reactions, a first-order dependence on the aromatic substrate exists; an equilibrium relationship consisting of four systems has been an equilibrium relationship consisting of four systems has been established among the products. The isomer distribution of the Cl-DPM which was formed by the cleavage of DPM or 4-Cl-DPM exhibited a marked variation with the reaction time. These results show that the cleavage reaction is closely connected with Friedel-Crafts benzylation.
  • Otohiko Tsuge, Masashi Tashiro
    1967 Volume 40 Issue 1 Pages 119-124
    Published: 1967
    Released: March 27, 2006
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    The benzylation of benzene and chlorobenzene with benzyl or p-chlorobenzyl chloride under the influence of various catalysts has been carried out in order to elucidate the relation between the cleavage reaction of the DPM and the Friedel-Crafts benzylation. In the aluminum chloride- or gallium chloride-catalyzed benzylation, the compositions of the equilibrium mixture are similar to those of the cleavage reaction. It has been suggested that, in the presence of such catalysts, the DPM formed at an initial stage is cleft with the catalyst, and that the same equilibrium relationship as has been postulated in the cleavage reaction is established. On the other hand, in the aluminum chloride-, gallium chloride-nitro compound complex or in indium chloride, which does not exhibit the ability to cleave the DPM, both the products and the isomer distributions are different. It has been estiablished that the isomer distributions in the benzylation are affected by the reactivity of the reactive species as well as by the catalytic ability to cleave the DPM. It has also been found that, under the influence of a strong catalyst such as the aluminum chloride - nitromethane complex, the relative reactivity of p-chlorobenzyl chloride on benzene is equal to that of benzyl chloride, while the reactivity of the former is about half that of the latter in the presence of such a weak catalyst as indium chloride.
  • Otohiko Tsuge, Masashi Tashiro
    1967 Volume 40 Issue 1 Pages 125-130
    Published: 1967
    Released: March 27, 2006
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    The cleavage reaction of DPM and Me-DPM, and the benzylation of toluene, have been carried out under various conditions. On the basis of the results of this series, the correlations with the cleavage reaction of the DPM and with the Friedel-Crafts benzylation have been inclusively discussed. Furthermore, the mechanism of the isomerization of mono-substituted DPM under the influence of aluminum chloride has been suggested.
  • Yuzo Aito, Taku Matsuo, Chuji Aso
    1967 Volume 40 Issue 1 Pages 130-134
    Published: 1967
    Released: March 27, 2006
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    The configurational isomers of 2, 5-dimethoxytetrahydrofuran were synthesized as model compounds of the cyclopolymer of succinaldehyde. The NMR spectra of the isomers were then studied in carbon tetrachloride and in benzene. From the behavior of the methyl and methylene protons of the isomers in chemical shifts and in the formation of a “loose-complex” with benzene, it was concluded that the isomer with the lower boiling point had a trans configuration and that the isomer with the higher boiling point had a cis configuration. The NMR spectrum of 2, 5-dimethoxy-2, 5-dihydrofuran was similarly investigated in order to compare it with that of 2, 5-dimethoxytetrahydrofuran. The spectrum was rather simple; each signal was assigned to the cis or to the trans configurational isomer.
  • Akio Matsuda
    1967 Volume 40 Issue 1 Pages 135-144
    Published: 1967
    Released: March 27, 2006
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    The present reaction was studied in connection with our preceding research on the hydroesterification of propylene (This Bulletin, 38, 710 (1965)). The cobalt carbonyl-catalyzed reaction was successfully carried out in the presence of a small amount of hydrogen and a limited amount of pyridine; methyl esters of α- and β-cyanopropionic acids were thus obtained, the former in a larger amount than the latter. As the temperature decreased or as the partial pressure of carbon monoxide increased, the selectivity of the reaction toward the methyl α-cyanopropionate grew larger. The reaction mechanism was mainly investigated by kinetic methods. The infrared spectra of the catalyst solutions were measured at −60°C with a low-temperature cell. It was found by the IR study that acylcobalt carbonyls were formed in the acrylonitrile solution of dicobalt octacarbonyl and pyridine when it was treated under the same conditions (temperature and pressure) as in the reaction. It was found from the results of kinetic studies that the mechanisms of reactions at temperatures above and below 100°C were different; each of these mechanisms was discussed.
  • Shigehiro Ooba, Hiroshi Kato, Masaki Ohta
    1967 Volume 40 Issue 1 Pages 144-146
    Published: 1967
    Released: March 27, 2006
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    The nitrous acid deamination of 3-methylenecyclobutylcarbinylamine in water gave 2-methylenecyclopentanol and 3-methylenecyclopentanol. The reduction of methyl 3-methylene-cyclobutanecarboxylate with lithium aluminum hydride gave 3-methylenecyclobutylcarbinol.
  • Tamotsu Fujisawa, Yukio Yokota, Teruaki Mukaiyama
    1967 Volume 40 Issue 1 Pages 147-149
    Published: 1967
    Released: March 27, 2006
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    A further study of 1, 3-addition-type ring-opening polymerization has been attempted by using cyclic N-phenyl- and N-methylethyleneamino phenylphosphinites as monomers, each of those has a nitrogen atom in place of one of the two oxygen atoms in the ring structure of a cyclic phosphonite. They were prepared from phenylphosphonous dichloride and N-phenyl-and N-methylaminoethanols. The ring-opening 1, 3-addition reaction of the N-phenyl derivative with benzyl bromide, as a model experiment for the polymerization, has been found to proceed smoothly, giving the desired adduct, which in turn gave benzylphenylphosphinic acid and N,N′-diphenylpiperadine on hydrolysis. These cyclic aminophosphinites were then polymerized to give the expected poly(aminophosphine oxide) s in the presence of Arbusov reaction-type reagents or in the absence of a catalyst at elevated temperatures.
  • Yoshio Iwakura, Fujio Toda, Yoshinori Torii
    1967 Volume 40 Issue 1 Pages 149-153
    Published: 1967
    Released: March 27, 2006
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    In the syntheses of 5-oxazolones (2-isopropenyl-4-alkyl-2-oxazolin-5-ones) from N-meth-acryloyl-α-amino acids, new isomerized oxazolones were obtained. By NMR spectroscopy, the structures of isomerized oxazolones were determined to be pseudoxazolones (2-isopropylidene-4-alkyl-3-oxazolin-5-ones). The NMR spectra of several pseudoxazolones were measured and compared with the normal oxazolones.
  • Shichiro Kakimoto, Shuichi Tonooka
    1967 Volume 40 Issue 1 Pages 153-159
    Published: 1967
    Released: March 27, 2006
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    Attempts to prepare 5, 6-dihydropyrido[2, 3-d]pyridazin-8(7H)-one by the hydrogenation of pyrido[2, 3-d]pyridazin-8(7H)-cne were not successful, but it was found that the hydrogen-ated compound was 1, 2, 3, 4-tetrahydropyrido[2, 3-d]pyridazm-8(7H)-one. The same reaction occurred in the case of pyrido[2, 3-d]pyridazin-5(6H)-one and some other derivatives.
  • Masao Iwamoto, Sadao Yuguchi
    1967 Volume 40 Issue 1 Pages 159-162
    Published: 1967
    Released: March 27, 2006
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    The crystalline polymer has been obtained by polymerizing 2-butene using a Ziegler-type catalyst containing titanium trichloride. 2-Butene was transformed into an equilibrium mixture of 1-butene and cis- and trans-2-butene by the catalytic action of titanium trichloride. When alkylaluminum was present in the system, isotactic poly-1-butene was obtained. These results can be explained by the concept of isomerization polymerization.
  • Tadao Inoue, Kikuhiko Koyama, Toru Matsuoka, Shigeru Tsutsumi
    1967 Volume 40 Issue 1 Pages 162-168
    Published: 1967
    Released: March 27, 2006
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    The electrochemical oxidation of methanol and ethanol in the presence of trans-stilbene, cis-stilbene, norbornene, and styrene has been studied. The major gaseous and nongaseous products have been identified and determined, and the corresponding dimethoxylated derivatives and diethoxylated derivatives have been obtained in fairly high yields. The main path by which these products may have arisen has been discussed, and the stereochemistry of the addition of methoxy radicals to stilbene has been discussed. Particular attention has been given to the possibility that the main product arises from the anodic oxidation of an intermediate radical to a carbonium ion.
  • Koko Maeda, Taro Hayashi
    1967 Volume 40 Issue 1 Pages 169-173
    Published: 1967
    Released: March 27, 2006
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    In order to study the mechanism of the chemiluminescence of lucigenin which was emitted with hydrogen peroxide in an alkaline solution, the color and the spectrum of the chemiluminescence and fluorescence, the spectrum of absorption, and the electron spin resonance were investigated. The color of the chemiluminescence was found to vary from green to blue with a decrease in the concentration of lucigenin. The spectrum of the blue chemiluminescence spread over only a visible region of 420—650 m/μ, with a peak at 485 mμ. With an increase in the concentration of lucigenin, the peak shifted to 510 m/μ or longer, corresponding to the green color of the chemiluminescence. This shift is due to self-absorption by lucigenin. The fluorescence spectrum of lucigenin in aqueous sodium hydroxide showed a peak at 508 mμ. The peak gradually disappeared, and the spectrum eventually showed new peaks at 435 and 450 m/μ which almost agreed with the peaks of the fluorescence spectrum of 10-methylacridone. Lucigenin exhibited an electron spin resonance of a single peak (g-value 2.004) in a solid state. These results show that the chemiluminescence of lucigenin is neither of the fluorescence of lucigenin nor that of 10-methylacridone yielded in the chemiluminescent solution of lucigenin and that the mechanism of the chemiluminescence is likely to involve a free radical intermediate.
  • Tsutomu Matsuda, Masahiko Sugishita
    1967 Volume 40 Issue 1 Pages 174-177
    Published: 1967
    Released: March 27, 2006
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    The reaction of cyclooctatetraene oxide with ethylmagnesium bromide, phenylmagnesium bromide and t-butylmagnesium bromide was found to yield 2, 4, 6-cycloheptatrienyl-1-ethyl-, phenyl- and t-butylcarbinol respectively. The treatment of cyclooctatetraene oxide with a catalytic amount of magnesium bromide in ether afforded phenyl acetaldehyde in a 76% yield. The dehydration of the carbinols with a catalytic amount of p-toluenesulfonic acid resulted in their further rearrangement to trans-β-substituted styrenes.
  • Kazuhiro Hirota, Yoshiharu Izumi
    1967 Volume 40 Issue 1 Pages 178-181
    Published: 1967
    Released: March 27, 2006
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    The racemization of amino acid catalyzed by several derivatives of o-nitrosophenol in the presence of metal ion was studied in a non-enzymatic system. The racemizations of L-alanine with 1-nitroso-2-naphthol, 2-nitroso-l-naphthol, 2, 4-dinitrosoresorcinol and disodium 1-nitroso-2-naphthol-3, 6-disulfate as catalysts were measured in the presence of metal ion and their activities were compared using various metal ions in these racemizations. Furthermore, racemizations with 1-nitroso-2-naphthol were carried out at various pH values in the presence of cupric or zinc ion and the optima pH values were measured. The racemization activities of 1-nitroso-2-naphthol and 4-nitroso-1-naphthol were compared to elucidate the relationship between the structural features and the activities of these catalysts. A possible mechanism for the catalytic racemization of amino acids is discussed briefly.
  • Kazuhiro Hirota, Kunihiko Miyamoto, Yoshiharu Izumi
    1967 Volume 40 Issue 1 Pages 182-184
    Published: 1967
    Released: March 27, 2006
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    The catalytic racemization of amino acids with aurintricarboxylic acid was examined in the presence of cupric ion. The tests were conducted at various pH values to study the optimum pH for the racemization. Moreover the racemizations with aurintricarboxylic acid and with o-cresolphthalein were compared and the results are briefly discussed with regard to the relationship between the structural features and the activities of these catalysts.
  • Hiroo Inoue, Yasuji Kida, Eiji Imoto
    1967 Volume 40 Issue 1 Pages 184-190
    Published: 1967
    Released: March 27, 2006
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    Copper-iron-polyphthalocyanine shows catalytic activity on the oxidation of acetaldehyde ethylene acetal with oxygen at 30°C; this catalytic activity is remarkably dependent on the atomic ratio of copper to iron ions involved and on the activation energy of the electrical conductivity of copper-iron-polyphthalocyanine. The catalytic oxidation of acetaldehyde ethylene acetal with oxygen in the presence of copper-iron-polyphthalocyanine gives, selectively, ethylene glycol monoacetate as the main reaction product, together with small amounts of ethylene glycol diacetate, ethylene glycol, acetaldehyde, and acetic acid. This catalyst is also effective in the selective oxidation of cumene and benzaldehyde ethylene acetal.
  • Tamotsu Fujisawa, Hajime Koda, Teruaki Mukaiyama
    1967 Volume 40 Issue 1 Pages 190-193
    Published: 1967
    Released: March 27, 2006
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    Poly(ethylene N-chlorocarbamate) was obtained by the 1,4-addition-type ring-opening polymerization of ethylene N-chloroiminocarbonate with cationic catalysts, such as boron trifluoride etherate or sulfuric acid. Although it is an amorphous, tough elastomer, it is unstable in the air and decomposes to a brittle, pumiceous polymer. The reductions of polyethylene N-chlorocarbamate) by means of an aqueous solution of arsenic trioxide, butanol-zinc powder, t-butanol, and fluorene gave poly(ethylene carbamate), which is a new, stable, hydrogen-bonded polymer.
  • Kazuhiko Yamamoto, Yoshio Matsushima
    1967 Volume 40 Issue 1 Pages 194-196
    Published: 1967
    Released: March 27, 2006
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    In the course of the study of the substrate specificity of egg white lysozyme, a phenyl glycoside of a disaccharide, N-acetyl-β-D-glucosaminyl(1→6)N-acetyl-muramic acid, was synthesized as a model substrate of the enzyme. Evidence for the 1→6 linkage between two component sugars was obtained by chemical and NMR studies. As a reference standard for a chromatographic investigation, 4-O-methyl muramic acid was prepared. The lysozyme action on the model substrate, if any, was found to be extremely weak.
  • Jiro Tsuji, Shinzo Imamura
    1967 Volume 40 Issue 1 Pages 197-201
    Published: 1967
    Released: March 27, 2006
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    A general method of synthesizing a new type of π-allylic complex of palladium from compounds with an allylic hydrogen activated by a carbonyl group is described. Ethyl 3-butenoate and ethyl 2-butenoate give the same carbethoxy-substituted π-allyl complex, with hydrogen chloride eliminated, when treated with palladium chloride. Unsaturated diesters, such as diethyl glutaconate and diethyl 3-hexenedioate, also react with palladium chloride to give the corresponding π-allylic complexes. The structures of these complexes are discussed by means of a study of their NMR spectra. The carbonylation of these complexes proceeds smoothly, and carbon monoxide is introduced to form unsaturated esters. 3-Butenoate and then glutaconate are prepared, starting from allyl chloride, by a series of complex formations and carbonylation reactions. The possible synthetic application of this method of step-by-step introduction of carbon monoxide to other olefins is suggested. Diethyl 3-hexenedioate gives the complex, which is then converted into diethyl muconate by the elimination of palladium by the action of a base or carbon monoxide.
  • Hiroshi Minato, Atsushi Fujii
    1967 Volume 40 Issue 1 Pages 202-203
    Published: 1967
    Released: March 27, 2006
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    Rates of methanolysis of thionyl chloride and methyl chlorosulfite were measured conductimetrically at +1.0–−91.6°C, and were compared with the rates of other acid chlorides. Activation enthalpies and entropies were obtained.
  • Motonori Ohno, Tetsuo Kato, Nobuo Mitsuyasu, Michinori Waki, Satoru Ma ...
    1967 Volume 40 Issue 1 Pages 204-208
    Published: 1967
    Released: March 27, 2006
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    A protected undecapeptide containing the possible N-terminal sequence of ribonuclease T1, namely benzyloxycarbonyl-L-alanyl-S-benzyl-L-cysteinyl-L-asparaginyl-L-tyrosyl-L-threonyl-S-benzyl-L-cysteinyl-glycyl-L-seryl-L-asparaginyl-S-benzyl-L-cysteinyl-L-tyrosine ethyl ester (XXI), was synthesized by coupling of benzyloxycarbonyl-alanyl-S-benzylcysteinyl-asparaginyl-tyrosine azide with heptapeptide ester, threonyl-S-benzylcysteinyl-glycyl-seryl-asparaginyl-S-benzylcysteinyl-tyrosine ester, which is derived from p-methoxybenzyloxycarbonyl-heptapeptide ester by the action of trifluoroacetic acid. The optical homogeneity of the protected undecapeptide (XXI) was established by deblocking of XXI and subsequently digesting the resulting free undecapeptide with leucine aminopeptidase.
  • Sumio Umezawa, Mitsuhiro Kinoshita, Hiroaki Yanagisawa
    1967 Volume 40 Issue 1 Pages 209-214
    Published: 1967
    Released: March 27, 2006
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    The reactions of α, β-unsaturated α-nitroesters with dienes produced cyclic α-nitroesters. In all cases, a mixture of diastereoisomers was obtained. Catalytic hydrogenation, followed by hydrolysis, gave a number of cyclic α-amino acids which are closely related to natural terpenes. The NMR spectra of some of these compounds were useful in making structural assignments.
  • H. K. L. Gupta, M. R. Bhandari, N. C. Sogani
    1967 Volume 40 Issue 1 Pages 215-217
    Published: 1967
    Released: March 27, 2006
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  • P. Sanyal, S. P. Sangal, S. P. Mushran
    1967 Volume 40 Issue 1 Pages 217-221
    Published: 1967
    Released: March 27, 2006
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  • C. M. Gupta
    1967 Volume 40 Issue 1 Pages 221-222
    Published: 1967
    Released: March 27, 2006
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  • Ayako Torikai, Kenji Fueki, Zen’ichiro Kuri
    1967 Volume 40 Issue 1 Pages 223-224
    Published: 1967
    Released: March 27, 2006
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  • Michio Kobayashi, Akira Yabe
    1967 Volume 40 Issue 1 Pages 224-225
    Published: 1967
    Released: March 27, 2006
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  • Tadayuki Ohmae, Shun-ichi Ohnishi, Keiji Kuwata, Hiroshi Sakurai, Isam ...
    1967 Volume 40 Issue 1 Pages 226-227
    Published: 1967
    Released: March 27, 2006
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