Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 43 , Issue 11
Showing 1-50 articles out of 74 articles from the selected issue
  • Akio Furusaki, Yujiro Tomiie, Isamu Nitta
    1970 Volume 43 Issue 11 Pages 3325-3331
    Published: 1970
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The absolute configuration of bromoanhydrotetrodoic lactone, C11H14O7N3Br, has been determined on the basis of an X-ray study of its hydrobromide. The crystals are orthorhombic, with four chemical units in a unit cell of these dimensions: a=10.88±0.04, b=15.95±0.05, and c=8.55±0.03 Å; the space group is P212121. The observations for Bijvoet inequalities were made on equi-inclination integrating Weissenberg photographs taken with CuKα radiation around the a axis. On the other hand, the calculations were carried out with the parameters at the stage of the R factor of 11.9% and with anomalous dispersion correction of −0.9 for ΔfBr and 1.5 forΔfBr . The observed and calculated inequalities for ten pairs of reflections were all in agreement with each other, so the absolute configuration was determined without any uncertainty. In addition to the X-ray determination of the absolute configuration mentioned above, the present paper will describe the details of the crystal and molecular structure.
  • Akio Furusaki, Yujiro Tomiie, Isamu Nitta
    1970 Volume 43 Issue 11 Pages 3332-3341
    Published: 1970
    Released: March 27, 2006
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    The crystal and molecular structure of the hydrobromide of tetrodotoxin itself, C11H17O8N3·HBr, have been studied by means of three-dimensional X-ray analysis. The crystals are tri-clinic, with two formula units in a unit cell of the dimensions; a=8.79, b=9.02, c=9.51 A, α=106°51′, β=88°1′, and γ=96°23′; the space group is pl. The intensities of reflections were recorded on equi-inclination Weissenberg photographs taken with CuKα radiation around the b and c axes, and were measured visually with a calibrated intensity scale. The structure was elucidated by means of the Fourier and least-squares methods, and was refined by the block-diagonalmatrix least-squares method, the anisotropic thermal motion being assumed only for bromine atoms. The stereostructures of the two crystallographically-independent molecules of tetrodotoxin thus obtained are almost identical and correspond to that deduced by Tsuda et al., by Hirata et al., and by Woodward et al., all in 1964. It is noteworthy that, in both of the two molecules, the C–O distance for the free hydroxyl group in the ortho-ester part (1.36 and 1.39 Å) is somewhat smaller than the ordinary aliphatic C–O distance, 1.43±0.01 Å, and that it is rather closer to the phenolic C–O distance, 1.36±0.01 Å.
  • Shin Tsuge, Hajime Ito, Tsugio Takeuchi
    1970 Volume 43 Issue 11 Pages 3341-3344
    Published: 1970
    Released: March 27, 2006
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    The distribution of chlorine atoms in radically chlorinated polystyrenes was studied by means of pyrolysis gas chromatography. Degradation products such as styrene, benzene, toluene and chlorobenzenes are related to different structures of the chlorinated polymers. The sequence distribution of each structure was discussed over a wide range of degree of chlorination. Chlorine atoms are first substituted with α- then β-hydrogen in the main chain of polystyrene. The first ring substitution of chlorine occurs competitively at p-position even before both α- and β-hydrogens are substituted.
  • Mamoru Kamiya
    1970 Volume 43 Issue 11 Pages 3344-3353
    Published: 1970
    Released: March 27, 2006
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    The semiempirical Pariser-Parr-Pople SCF method combined with configuration-interaction has been applied for calculation of the electronic spectrum, ionization potential and electron affinity, π-electron distribution and total π-energy of such heterocycles as oxazole, isoxazole, oxadiazoles, imidazole, pyrazole, triazoles and their monobenzo-derivatives, and the theoretical results have been compared with the available spectral data and miscellaneous chemical properties including the position-dependency on substitution reactions, novel photochemical isomerization of several compounds and so forth.
  • Yasuaki Okamoto, Toshinobu Imanaka, Shiichiro Teranishi
    1970 Volume 43 Issue 11 Pages 3353-3357
    Published: 1970
    Released: March 27, 2006
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    The distribution of the acid strength on two zeolites, 13X and 10X, and on the copper form of X-type zeolite were estimated from the differential heats of n-butylamine adsorption in a benzene solution. The acid sites on these zeolites were revealed to have two kinds of acid strengths, that is, the cation-dependent one and the cation-independent one. The former corresponds to the stronger acid strength, and the latter, to the weaker. The IR spectra of the residual surface OH groups on these catalysts were also investigated. The strongest acid sites on each zeolite were considered to be those of the cation-dependent OH group which has the lowest frequency. The interaction between surface OH groups and immersed benzene was assumed to be a π-type hydrogen bond.
  • Shiro Konishi, Shigeya Niizuma, Masao Koizumi
    1970 Volume 43 Issue 11 Pages 3358-3363
    Published: 1970
    Released: March 27, 2006
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    ESR spectra of radical anions produced by bringing 9-chloro-, 2,7-dibromo-9-chloro-, and 2,4,5,7-tetrabromo-9-chloroacridine into contact with alkali metal (sodium and potassium) in tetrahydrofuran were measured at room temperature and/or at lower temperatures, and the analysis of them was made by means of a simulation method. Hyperfine coupling constants of acridine anion radicals, produced by the similar method in tetrahydrofuran and also by the electrolytic reduction in acetonitrile with the flow method, were determined, taking those of halogen derivatives into consideration. ESR spectra of acridine and 9-chloroacridine anion radical were found to involve the coupling of sodium, showing that these radicals were in the form of ion pair. The coupling constants of bromoacridine anion radicals did not give any difference between the sodium and the potassium reduction. The couplings of halogen atoms were not observed. Good agreement was obtained between the coupling constants calculated from spin densities and those determined experimentally. In general, the solution of radical anions of halogenides gradually yields brownish aggregates at lower temperatures (−20∼–30°C), their ESR spectra becoming weaker and unresolved. The temperature change is reversible and qualitatively resembles the behavior of acridine anion radical.
  • Yoshio Iwadare
    1970 Volume 43 Issue 11 Pages 3364-3372
    Published: 1970
    Released: March 27, 2006
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    In order to study the surface-adsorption behavior of anionic surfactants on fibers, the ζ-potentials of some synthetic fibers in aqueous solutions of sodium alkyl sulfates and their mixtures mainly above the critical micelle concentration (CMC), were measured. Further, the viscosities of aqueous solutions of pure surfactants were determined. Consequently, it can be presumed, on the basis of the viscosity data, that the structure of the micelles of these agents varies at the break of the ηspmcm vs. cm curve. The ζ-potentials (negative) of fibers in aqueous solutions of the agents rapidly changed with an increase in the agent concentrations, but it remained nearly constant above the CMC. At much higher concentrations, the ζ values gradually changed; thereafter, passing a break or a minimum, they became approximately constant again. The concentration at the break or the minimum observed nearly corresponded to that at the break of the ηspmcm vs. cm curve. It may, therefore, be suggested that the change in ζ-potentials at high concentrations is connected with that in the structure of the micelles. The ζ-potentials (negative) of fibers in aqueous mixed solutions changed sharply with an increase in the concentration of the mixtures and thereafter, passing a maximum in the vicinity of the CMC, complicatedly changed as the total concentrations and mixing ratios changed.
  • Akira Kuboyama
    1970 Volume 43 Issue 11 Pages 3373-3376
    Published: 1970
    Released: March 27, 2006
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    The phosphorescence bands of anthraquinone in the solvents used in this work are all safely assigned to the π*n bands on the basis of their short lifetimes. In n-paraffins (n-hexane, n-heptane, and n-octane), two phosphorescence bands which are close to each other are found. Considering the dependence of the relative intensities of these two phosphorescence bands on the carbon-numbers of the n-paraffins, it is assumed that the longer- and the shorter-wavelength bands are due to the anthraquinone molecules with the C–O bond axis parallel to and perpendicular to the longitudinal axis of the planar zig-zag form of the n-paraffin molecules in the n-paraffin crystals respectively. In chloroform and dioxane, a broad phosphorescence band shows a blue-shift relative to the corresponding band in the alkane solvents. In chloroform a sharp phosphorescence band was also observed for a solution which was rapidly cooled. This sharp band is assumed to be due to the anthraquinone molecules with a certain geometry relative to the surrounding chloroform molecules.
  • Takemi Yamamura, Akinori Hasegawa, Yoshio Yamada, Masaji Miura
    1970 Volume 43 Issue 11 Pages 3377-3382
    Published: 1970
    Released: March 27, 2006
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    The behavior of the Mn2+ ion on the surface of MgO was studied by using the ESR technique. The powder of MgO, the surface of which was doped with the Mn2+ ion, was calcined at different temperatures from 100 to 1000°C in a vacuum, and then the ESR spectra were observed at room temperature. It was noticed that the spectral intensity showed a minimum at about 500°C, that the zero-field splitting parameter, D, increased with the temperature, and that the hyperfine coupling constant, A, decreased enormously at about 700°C. The environments around the Mn2+ ion on the surface of MgO were discussed on the basis of these results. When H2, CO, or O2 was added after the calcination, the D and A values changed in the temperature range above 500°C. Especially when O2 was introduced, the D value fell to zero upon treatment at 1000°C. The crystal field around the Mn2+ ion and the bonding between the Mn2+ ion and its environments were discussed by taking into account the results of the magnetic-susceptibility measurements of the manganese ion on MgO.
  • Satoru Tsuda, Akira Yokohata, Toshikatsu Umaba
    1970 Volume 43 Issue 11 Pages 3383-3390
    Published: 1970
    Released: March 27, 2006
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    The negative ion mass spectra from alkyl (methyl, ethyl, n- and iso-propyl) cyanides with electron energies of 80 eV, 40 eV and 9.5 eV were measured by a Hitachi RMU-6D mass spectrometer with emphasis on the relative abundance of negative ions to positive ions with electron energies of 80 eV, 40 eV and 15 eV. In every sample, the electron impacts with 80 eV and 40 eV gave almost the same distribution of me for negative ion mass spectra. Then, the peak of me 26(CN ) ions was the most intense and also the relatively strong peak of 25(C2H) ions was found through all samples. On the other hand, the formations of 38(C2N), 39(CHCN) and 41(CH3CN) ions from methyl cyanide, of 50 (C3N) ions from ethyl cyanide, n- and iso-propyl cyanides, of 40(CH2CN) ion from n-propyl cyanide were characteristic of each sample. The ratio of the yield of negative ions to positive ions was respectively of the order of ∼104 for CH3CN+/CN (CH3CN), C2H4+/CN (C2H5CN), C3H5+/CN (n-C3H7CN) and C3H6+/CN (iso-C3H7CN) at 80 eV and 40 eV electron energies. At 9.5 eV, me 26 (CN) ions predominated over other negative ions for all the samples and a much larger peak of 40 (CH2CN) ions in n-C3H7CN than in iso-C3H7CN was also observed. Then, we got the values of 19∼65 for CH3CN+/CN, C2H4+/CN, C3H5+/CN and C3H6+/CN (15 eV for positive ions). This work also gave linear relationship of the yield of each negative ion to the pressure in the range used for an usual chemical analysis.
  • Hideo Akutsu, Masamichi Tsuboi
    1970 Volume 43 Issue 11 Pages 3391-3399
    Published: 1970
    Released: March 27, 2006
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    Copolymers of riboadenylic and riboguanylic acids (poly A,G) with guanylic acid contents of 8.5–29.6% were prepared. The ultraviolet and infrared absorptions were examined of aqueous solutions of mixtures of poly A,G and polyribouridylic acid (poly U) of various mole ratios. It has been shown that in a solvent with 0.1 M Na+ a triple-helical structure is formed with a (Remark: Graphics omitted.) type inter-base binding as well as a double-helical structure with a A···U type binding, while in a solvent with 0.01 M Na+ only double-helical structure is formed. A guanine residue in the copolymer remains within the helix structure when its neighbors are mostly adenine residues, whereas it rotates out when there are many guanine residues in its vicity. On heating the solution, the structures just mentioned were found to be broken. The process of such a breaking down was followed also by means of the ultraviolet and infrared absorption measurements.
  • Toyoaki Kimura, Mitsuharu Fukaya, Minoru Hada, Terunobu Wakayama, Kenj ...
    1970 Volume 43 Issue 11 Pages 3400-3404
    Published: 1970
    Released: March 27, 2006
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    The effect of chloromethanes (CH2Cl2, CHCl3 and CCl4) on hydrogen formation from γ-irradiated methylcyclohexane (MCH) and 3-methylpentane (3MP) at −196°C was investigated. It was found that the decrease in hydrogen yield by the presence of CH2Cl2 was almost the same as that caused by an electron scavenger such as N2O, n-butyl chloride, SF6 or iodobenzene, but the hydrogen yield was much lower in the presence of CHCl3 or CCl4 than other electron scavengers. Although the yield of CCl3. radicals formed from dissociative electron attachment to CCl4 in CCl4-MCH systems was ∼1.4G, the decrease in hydrogen yield was ∼3G. A similar result was obtained for CHCl3-MCH systems. Thus we have ascribed the effect of CH2Cl2 on hydrogen formation to electron scavenging and that of CHCl2 or CCl4 to excitation transfer as well as electron scavenging. ESR studies on radical formation from these systems also support the above interpretation.
  • Chihiro Dehari, Yoshio Matsunaga, Kensuke Tani
    1970 Volume 43 Issue 11 Pages 3404-3409
    Published: 1970
    Released: March 27, 2006
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    The diffuse reflection spectra of sixteen 1-arylazo-2-naphthols diluted with sodium chloride were measured at concentrations of 1, 0.1, and 0.01% in the range from 350 to 700 mμ. The spectra indicate the coexistence of the azo and hydrazone tautomers in this solid, two-component system. Moreover, the spectra were found to be markedly modified in many cases by elevating the temperature, especially at a concentration of 0.01%. These changes were shown to be thermally reversible and were attributed to the movement of the tautomeric equilibrium. The direction depends upon the kind and position of the substituents, e.g., towards the hydrazone tautomer in the case of the p-Cl and o-NO2 derivatives and towards the azo tautomer in the case of the p-NO2 and o-OH derivatives. It was suggested that the present systems are not simple mixtures of pulverized 1-arylazo-2-naphthols and sodium chloride, but that some fraction of the organic components is well dispersed and adsorbed on the highly polar surface of the alkali halide.
  • Motoyuki Tsuda, Hiroo Inokuchi
    1970 Volume 43 Issue 11 Pages 3410-3414
    Published: 1970
    Released: March 27, 2006
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    Homogeneous and heterogeneous mechanisms of parahydrogen conversion and hydrogen-deuterium exchange reactions were investigated in the presence of benzonitrile–cesium ion radical salt. Studies of their activation energies and rate constants showed that the heterogeneous reaction on the solid-ion radical salt occurs mainly through the “chemisorption mechanism” and the “exchange mechanism”, but the homogeneous reaction over the salt solution in benzonitrile takes place only through the “physical mechanism.” According to these results, it was concluded that the catalytic activity and reactivity of the ion-radical salt must be due to the nature of its solid phase, not to that of its aromatic anion or free-ion radical pair.
  • Motoyuki Tsuda
    1970 Volume 43 Issue 11 Pages 3415-3419
    Published: 1970
    Released: March 27, 2006
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    The para-orthohydrogen conversion (rate constant keH and the deuterium exchange reaction (rate constant keD) over the benzonitrile-alkali metal ion radical salt were investigated as functions of the donor component–alkali metal. The sort of alkali metals in the ion radical salts greatly affected the catalytic activity and the reactivity. The activation energies obtained from the temperature dependence of keH and keD, EH and ED, and the value of α(depending on the ratio of keH to keD monotonously decreased as Na→K→Rb, but those values showed an irregular trend for the Cs-complex. The results suggest that the catalytic activity cannot be understood only in terms of the nature of the components; must also be considered the structural nature of the solid phase of the ion radical salt.
  • Reita Tamamushi, Shojiro Goto
    1970 Volume 43 Issue 11 Pages 3420-3424
    Published: 1970
    Released: March 27, 2006
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    The membrane concentration potentials across a permselective sulfonated polystyrene collodion-base membrane were measured with aqueous solutions of alkali-metal salts at 25.0°C. By assuming the ideal behavior of the membrane, the activity coefficients of the critical cations were determined from the membrane concentration potentials at ionic strengths higher than 0.01. The ion activity coefficients of alkali-metal cations were found to follow the order Li+>Na+>K+ for the chlorides, nitrates, perchlorates, and sulfates. The order of activity coefficients of Na+ in different halide solutions was bromide>chloride>fluoride. Considerable differences were observed between the individual and mean activity coefficients at ionic strengths higher than 0.01. The individual ion activity coefficients determined from the experimental data were analysed by means of the extended Debye-Hückel eauation.
  • Yoko Ono, Inosuke Koyano, Yuji Mori, Ikuzo Tanaka
    1970 Volume 43 Issue 11 Pages 3425-3434
    Published: 1970
    Released: March 27, 2006
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    Chemi-ionization has been studied by the collision of the excited atom of cesium (82P1⁄2), whose energy is lower by 0.7 eV than its ionization energy, with cesium, rare gases or simple molecules. The mechanisms for the chemi-ionization, and quenching processes occurring simultaneously were set up and the cross sections of the processes have been determined. Since the pressure effects of added gases to the absorption coefficient of Cs at 3888 Å from the He lamp could not be neglected, suitalbe corrections were made.
  • Yoshikatsu Miyashita, Shigeya Niizuma, Hiroshi Kokubun, Masao Koizumi
    1970 Volume 43 Issue 11 Pages 3435-3443
    Published: 1970
    Released: March 27, 2006
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    The photoreduction of acridine in tetrahydrofuran (THF) has been investigated by the steady light experiment and also by the flash technique. The quantum yields in the aerated and deaerated solution were 0.12 and 0.36 respectively. The former value is referred to molecular mechanism while the difference of the two, 0.24, to radical mechanism. It was established that the sensitized reaction occurs with biacetyl (T(n–π*), 19700cm−1) as a triplet energy donor. The probability factor β with which the produced T(π–π*) of acridine (15840 cm−1) reacts with THF was found to be \gtrsim0.6. Anthracene T(π–π*), 14700cm−1) was found to act as a triplet energy acceptor and to reduce the photoreduction. From the decrease of the quantum yield caused by the addition of anthracene, the quantum yield via the lowest T(π–π*) of acridine was evaluated as 0.06. By combining this value with the above β-value, the apparent \varphiST has proved to be \lesssim0.1. This very small value compared with the \varphiST values presented for other solvents (benzene\gtrsim0.25, water\gtrsim0.24, ethanol\gtrsim0.29) leads to the conclusion that in THF, T(n–π*) is also a reactive state for the photoreduction. Further, an interesting aspect of the radical mechanism was elucidated from the comparison of ΦR (quantum yield due to radical mechanism) and ΦO2 (quantum yield of oxygen consumption).
  • Nobuaki Kanamaru, Saburo Nagakura
    1970 Volume 43 Issue 11 Pages 3443-3449
    Published: 1970
    Released: March 27, 2006
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    The π-electron structures of neutral aromatic ketyl radicals and their related hydrocarbon radicals were studied theoretically by combining the open-shell SCF MO method with the configuration-interaction calculation. The observed absorption bands of these radicals were well explained by the present theoretical study. From a comparison of the calculated transition energies and intensities with the observed values, it was concluded that the longest and second longest wavelength bands of the benzyl radical and the second longest wavelength band of the diphenylmethyl radical shift to shorter wavelengths upon hydroxy substitution. This may be regarded as characteristic of the substituent effect upon the absorption bands of aromatic radicals. The calculated spin densities were found to be consistent with the reactivity of the ketyl radicals in the formation of pinacols.
  • Mu-Chang Shieh, Kenichi Katabe, Taijiro Okabe
    1970 Volume 43 Issue 11 Pages 3449-3452
    Published: 1970
    Released: March 27, 2006
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    The decomposition of tetrasulfur tetranitride in an aqueous ammonia solution has been investigated. Ammonolysis of tetrasulfur tetranitride gives thiosulfate, sulfite, sulfate and sulfamate through the intermediate compound of trithionate. An increase in the concentration of ammonia raises the yield of sulfamate and lowers that of sulfate, but gives no remarkable change in the yield of thiosulfate. Besides this, in a concentration of ammonia higher than 15 N at 100°C an explosive reaction takes place. Addition of copper ion improves the yield of sulfamate, and the sulfite ion reacts with tetrasulfur tetranitride in an ammonia aqueous solution to form sulfate and sulfamate ion quantitatively.
  • Masaaki Muroya, Seiichi Kondo
    1970 Volume 43 Issue 11 Pages 3453-3456
    Published: 1970
    Released: March 27, 2006
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    The effects of various kinds of inorganic salts upon the physical properties of silica gel heated in the range up to 1200°C were studied. We measured the polymorphic behavior by means of X-ray diffraction, the simultaneous measurement of the differential thermal analysis, and the thermogravimetric analysis, and the specific surface area by means of the BET N2 method and by means of studying the water-adsorption capacity. The cationic impurities which were found to have strong effects upon the physical properties mentioned above are Na+, K+, Ca2+, Pb2+, Cd2+, Zn2+, and Sb3+. Cations such as Al3+, Cr3+, Mn3+, and Co2+ were shown to have weak but positive effects upon the physical properties of silica gel.
  • Yasuo Nakao, Hiroyuki Ishibashi, Akitsugu Nakahara
    1970 Volume 43 Issue 11 Pages 3457-3461
    Published: 1970
    Released: March 27, 2006
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    Eight new copper(II) complexes of SchifF bases derived from 2-acetylpyridine or pyridine-2-aldehyde and dipeptides containing glycine, β-alanine and/or α-aminoisobutyric acid have been prepared, and their relative stability was discussed on the basis of numerical data obtained by spectrophotometric, polarographic and other measurements. As a result, it was found that the stability of fused-ring systems decreases in the order 5-5-6-\simeq5-6-5->5-5-5->5-6-6-system (the first number represents the number of ring members containing pyridine derivatives and the second and third numbers represent those of ring members containing dipeptide moieties). The conclusion proposed previously that SchifF base chelates of aldehydes are generally less stable than those of corresponding ketones, has been proved to be valid also for the copper(II) chelates. It was found that transamination reactions take place in the copper(II) chelates of Schiff bases with pyridine-2-aldehyde and glycylglycine or glycyl-β-alanine.
  • Yoichi Sasaki, Junnosuke Fujita, Kazuo Saito
    1970 Volume 43 Issue 11 Pages 3462-3467
    Published: 1970
    Released: March 27, 2006
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    New binuclear cobalt(III) complexes of the type, [L2Co(μ-NH2,O2)CoL2](ClO4)n, where L is 1,10-phenanthroline or 2,2′-bipyridyl, and n=3 and 4, correspond to the so-called μ-peroxo and μ-superoxo form, respectively, were prepared and resolved into their optical isomers. Their absorption spectra have been compared with those of analogous ethylenediamine complexes and the structures have been discussed. The absolute configuration of these complexes has been determined by their circular dichroism spectra. The μ-peroxo complexes seem to be more stable than the corresponding μ-superoxo complexes in aqueous solution.
  • Nobuyuki Tanaka, Masahiro Kagawa
    1970 Volume 43 Issue 11 Pages 3468-3471
    Published: 1970
    Released: March 27, 2006
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    The thermal decomposition of CuBr2·2NH3 has been examined at the constant temperature, about 220°C. Copper(II) was reduced to copper(I), when bromine gas was found as one of the decomposition products, indicating that bromide anion may be the reducing agent for copper(II). The decomposition reaction of CuBr2 has been investigated by measuring the weight loss under the condition of the constant temperature. In a closed system, the reaction,
    CuBr_2(s)\leftrightarrowsγ-CuBr(s)+\frac12Br_2(g)
    attained to equilibrium, and ΔG° for this reaction was determined in the range from 160°C to 220°C to be given by the equation,
    ΔG°(cal.)=1.10×10^4-19.3 T (160°C–220°C).
    While the pressure of bromine gas was kept zero, CuBr2 decomposed following a first-order rate law in the beginning of the decomposition, and the activation energy was found to be 25.4 kcal/mol.
  • Hong Dae Shin
    1970 Volume 43 Issue 11 Pages 3472-3474
    Published: 1970
    Released: March 27, 2006
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    In order to obtain evidence for Tang’s hypothesis that pepsin (EC 3.4.4.1) forms a hydrophobic bond with the nonpolar side chain or its substrates, the inhibitory effect of carboxylic acids (from formic acid to isobutyric acid) on the activity of pepsin to the synthetic dipeptide, N-carbobenzoxy-L-glutamyl-L-tyrosine, was studied. Kinetic study showed that the inhibition by carboxylic acids was of competitive type. The inhibitor constant Ki decreased with an increase in the size of the inhibitor molecule. The free energy change of formation of complex between pepsin and hydrocarbon chain of carboxylic acid, −ΔFHC, increased linearly with the increase in the number of carbon atoms in the hydrocarbon chain of the inhibitor. It was suggested that the hydrophobic interaction between the side chain of amino acid residues in the binding region of the active center of pepsin and the hydrocarbon side chain of the inhibitor was the cause of the inhibition.
  • Khan A. Javaid, Noboru Sonoda, Shigeru Tsutsumi
    1970 Volume 43 Issue 11 Pages 3475-3479
    Published: 1970
    Released: March 27, 2006
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    A drastic deviation from the usually accepted reaction path was observed when oxidation of olefins was carried out in acetic acid with selenium dioxide in the presence of concentrated sulfuric acid. Oxidation of cyclohexene gave a mixture of cis- and trans-1,2-diacetoxycyclohexane. It was shown that in the oxidation of cyclohexene the organoselenium intermediate which produced 3-acetoxy-1-cyclohexene on pyrolysis, is not the intermediate in the present reaction. A study on reaction variables, such as effect of molar ratio of cyclohexene to selenium dioxide, amount of sulfuric acid, and water, reaction time and temperature, was undertaken. The reaction was extended to 1-octene and 1-hexene. A general structure for the organoselenium compound produced in the oxidation of terminal olefins in acetic acid without sulfuric acid, has been proposed. On the basis of our data and some previous concepts a reaction scheme has also been given.
  • Hiroshi Onoue, Kyoji Minami, Kunio Nakagawa
    1970 Volume 43 Issue 11 Pages 3480-3485
    Published: 1970
    Released: March 27, 2006
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    Ortho metalation by palladium(II) was observed in the reaction of lithium tetrachloropalladate(II) with various aromatic aldoximes and ketoximes in methanol in the presence of sodium acetate. The obtained chloro-bridged complexes(7) possessed both ortho-attached palladiumcarbon σ-bonding and palladium-nitrogen coordinate bonding to oximes. Reactions of O-acyl and O-methyl oximes with lithium tetrachloropalladate(II) were also carried out. An ortho metalation was observed in the former case, but dichlorobis(O-methyl oxime)palladium(II) type complexes containing no palladium-carbon σ-bonds were predominantly formed in the latter case. The bridge-splitting reaction of chloro-bridged complexes with triphenylphosphine and the metathetic reaction with sodium bromide in acetone were carried out. In the case of potassium tetrachloroplatinate(II), an ortho metalation reaction was observed giving the complexes(10) but chloro-bridged complexes could not be isolated.
  • Masanao Oya, Mayumi Tomizawa, Keikichi Uno, Yoshio Iwakura
    1970 Volume 43 Issue 11 Pages 3486-3489
    Published: 1970
    Released: March 27, 2006
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    The relationships between the polymerization solvents and the conformation of the polypeptides formed were studied on the basis of the infrared absorption spectra and the X-ray diffraction diagrams of the polymers. Poly-L-α-amino-n-butyric acid and poly-L-n-valine, prepared in dimethylsulfoxide (DMSO) as a polymerization solvent, formed β-conformation, but the respective polypeptides obtained in acetonitrile had an α-conformation. The conformational structure of poly-L-α-amino-n-butyric acid changed from β to α upon reprecipitation from a solution in dichloroacetic acid with ether. On the other hand, the conformational structure of poly-DL-α-amino-n-butyric acid did not change upon reprecipitation from a solution in formic acid and dichloroacetic acid.
  • Mamoru Ai
    1970 Volume 43 Issue 11 Pages 3490-3495
    Published: 1970
    Released: March 27, 2006
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    In the present investigation, the vapor-phase partial oxidation of cis-2-butene, butadiene, and furan was carried out over V2O5 and V2O5-P2O5, (1 : 1.6 atomic ratio), with various contact times, at 350°C, and at the concentration of 0.6–1.6% in air, in order to elucidate the effect of phosphorus addition to V2O5, on the selectivity and mechanism of butene oxidation. Oxidation activity decreased remarkably with an increase in the phosphorus content. In the presence of phosphorus (P/V=1.6), selectivity for the C4H8→C4H6 step and C4H6→C4H4O step were considerably increased, from 46 to 88 and from 72 to 93 mol% respectively, while selectivity for the C4H4O→maleic anhydride (MA) step fell from 60 to 50 mol%, due to the increase in polymer formation. From the results, it was concluded that V2O5 and V2O5-P2O5 catalysts show similar oxidation activity with regard to butene, butadiene, and furan, and that the quantities of the intermediate products are fairly much affected by the activity of the catalyst as well as by the difference in reactivity between the starting material and the intermediate over the catalyst.
  • Yoshiyuki Kawase, Sachiko Hori
    1970 Volume 43 Issue 11 Pages 3496-3500
    Published: 1970
    Released: March 27, 2006
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    The acetylation of bz-chloro- and bz-bromo-2,3-dimethylbenzofurans with acetyl chloride and aluminum chloride in carbon disulfide at room temperature was studied; it was found that the acetylation occurred at the 6- or 4-position, which is activated by the furan ring, regardless of whether the halogen atom is at the o-, the m-, or the p-position. In the cases of 7-halo compounds, diacetylation occurred to give the 4,6-diacetyl compounds, and the migration of the bromine atom of 6-acetyl-5-bromo-2,3-dimethylbenzofuran and of the methyl ester of the corresponding carboxylic acid occurred, as a result of the action of aluminum bromide in carbon disulfide at room temperature, to give the 4-bromo compounds. The haloketones thus obtained were then converted to the corresponding carboxylic acids by the bromoform reaction.
  • Takashi Koyano
    1970 Volume 43 Issue 11 Pages 3501-3504
    Published: 1970
    Released: March 27, 2006
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    Chlorination of cis-and trans-2-butenes with cupric chloride yields a mixture of meso- and dl-2,3-dichlorobutanes with meso/dl ratio of about 60/40, which is almost independent of the starting olefin configuration. For cyclohexene, trans-1,2-dichlorocyclohexane is accompanied with the cis-dichloride, the amount of which depends upon the solvent polarities. In all cases the starting olefins and the product dichlorides are sufficiently stable under the reaction conditions. The results indicate that open ionic intermediates are involved in the chlorination of simple olefins in liquid phase reaction.
  • Kazuya Ohga, Taku Matsuo
    1970 Volume 43 Issue 11 Pages 3505-3510
    Published: 1970
    Released: March 27, 2006
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    The structures of the photodimers obtained from 4-hydroxycrotonic acid γ-lactone under several conditions were determined. The products of irradiations in the solution were a pair of anti dimers: one is a head-to-head cyclo-adduct, and the other a head-to-tail adduct. The corresponding product in the solid, state, on the other hand, was a head-to-head cyclo-adduct in the syn form.
  • Kiyotada Matsui, Sadaichi Murotani, Tetsuro Nojiri, Masatoshi Motoi
    1970 Volume 43 Issue 11 Pages 3511-3514
    Published: 1970
    Released: March 27, 2006
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    Treatment of acetic anhydride with aliphatic dibasic acid chloride in the presence of 3 equivalents of aluminum chloride in nitrobenzene at 50°C afforded a polymer with the structure assigned to poly-malonylpolymethylene, R–[(CH2)m–COCH2CO]n–(CH2)m–R, (R=–COOH and/or –COCH3, n=8–16). Polymalonyl-heptamethylene, -hexamethylene and -pentamethylene were prepared and their properties were recorded. The product obtained by the reaction of acetic anhydride with adipoyl chloride seems to have a few cross-linkings in its structure.
  • Otohiko Tsuge, Ichiro Shinkai
    1970 Volume 43 Issue 11 Pages 3514-3521
    Published: 1970
    Released: March 27, 2006
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    The reactions of benzylideneacenaphthenones with sulfonium ylides were studied extensively. Although the reactions of benzylidene- and p-methylbenzylideneacenaphthenone with dimethylsulfonium methylide gave only resinous materials, the p-chlorobenzylidene derivative condensed with the ylide to afford the corresponding spiroxirane compound in a good yield. In the reactions with dimethyloxosulfonium methylide and carbonyl-stabilized sulfonium ylides such as ethyl (dimethylsulfuranilidene) acetate and dimethylsulfonium phenacylide, benzylidene-acenaphthenones gave the corresponding spirocyclopropyl ketones in good yields. The products obtained in the latter reactions were established to be cis-cyclopropyl compounds on the basis of NMR spectral studies. On the other hand, ethoxycarbonylmethyleneacenaphthenone condensed with carbonyl-stabilized sulfonium ylides to give trans-cyclopropyl ketones. On the basis of these results, the reaction mechanism was discussed. Also, bis-2,2′-methyleneacenaphthenone reacted with ethyl (dimethylsulfuranilidene) acetate to give the bis-spirocyclopropyl ketone.
  • Akio Sonoda, Ichiro Moritani
    1970 Volume 43 Issue 11 Pages 3522-3527
    Published: 1970
    Released: March 27, 2006
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    The addition reactions of α-ferrocenylcarbenes (ferrocenyl, ferrocenylmethyl, and ferrocenylphenyl carbene) to 1,1 -diphenylethylene have been examined by means of the thermal decomposition of the corresponding acylferrocene tosylhydrazone sodium salts. Then, the reactivities of the ferrocenylcarbenes have been compared with those of the corresponding phenyl and p-anisylcarbenes. It has been found that, of the carbenes investigated, the ferrocenylcarbenes show the lowest reactivity in addition reactions to the olefin. It has been established by a study of the NMR spectra that, in the ferrocenylcyclopropanes only, there is a restricted rotation about the bond between ferrocenyl and cyclopropyl groups. On this basis, the reactivity of the ferrocenylcarbenes has been discussed in terms of the steric hindrance of the bulky ferrocenyl group.
  • Takeshi Nakai, Makoto Okawara
    1970 Volume 43 Issue 11 Pages 3528-3534
    Published: 1970
    Released: March 27, 2006
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    A wide spectrum of electrophilic reactivity has been shown by N,N-dimethyl-S,S′-dimethyldithiocarbamidium perchlorate (II). Results obtained reveal that II behaves toward nucleophiles as an ambident electrophile with two reactive sites, a centered electron-definicent carbon and S-methyl carbon atom. The electrophilic behavior of II has been compared with that of a cyclic analog, 2-dimethylamino-1,3-dithiolanylium ion, and of a sulfur analog, tris (methylthio)-carbonium ion. Attempts to utilize II for synthetic reactions were made. Reactions of II with active methylene compounds gave ketone N,S-acetals which are of great interest from the standpoint of structural chemistry. o-Phenylenediamine and o-aminophenol reacted with II to give 2-dimethylamino-benzimidazole and -benzoxazole, respectively, in good yields. The reactions may provide a new method of introducing 2-dialkylamino groups into these heterocycles. Reactions of II with two equivalents of primary amines afforded tetrasubstituted guanidines. Reactions of II with p-toluenesulfonylhydrazine and an enamine were also studied.
  • Fumio Toda, Kunihiro Kumada, Nobuo Ishiguro, Katsuhiko Akagi
    1970 Volume 43 Issue 11 Pages 3535-3539
    Published: 1970
    Released: March 27, 2006
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    The title compounds were prepared, and their physical and chemical properties were investigated. The reduction of the cyclobutenes with lithium aluminum hydride afforded halogenfree cyclobutane. The mechanism of the reduction is discussed. The cyclobutenes showed their K-bands in a wavelength region ca. 100 nm shorter than in the cases of the corresponding cyclobutanes. Furthermore, the K-band of the cyclobutenes is comparable to that of 1-phenylbuta-1,3-diene. On the basis of the electronic spectral data, a puckered structure was postulated for the cyclobutenes.
  • Eizo Matsumura, Takeo Nashima, Fumihide Ishibashi
    1970 Volume 43 Issue 11 Pages 3540-3542
    Published: 1970
    Released: March 27, 2006
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    The reaction of 2-chloromethylpyridine (Ia) and its homologs, 5-ethyl- (Ib), 6-methyl- (Ic), and 4-methyl-2-chloromethylpyridine (Id), with pyridine gave the corresponding 1-(2′-pyridylmethyl)-pyridinium chlorides (II), from which, on heating with dimethyl sulfate, 1-methyl-2-(pyridiniomethyl)-pyridinium salts (III) were obtained. The pyridinium salts were treated with aqueous alkali at a low temperature to yield 1-methyl- (IVa), 5-ethyl-1-methyl- (IVb), 1,6-dimethyl- (IVc), and 1,4-dimethyl-2-pyridone (IVd). The reaction sequence, in combination with the 1-oxidation of 2-picolines and followed by the reaction of the 1-oxides with tosyl chloride to yield 2-chloromethylpyridines, is recommended as a convenient route for the synthesis of 1-methyl-2-pyridones starting with 2-picolines.
  • Otohiko Tsuge, Sumio Iwanami
    1970 Volume 43 Issue 11 Pages 3543-3549
    Published: 1970
    Released: March 27, 2006
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    The reactions of benzoylmethanesulfonyl chloride with various anils (Ar–CH=N–R) in the presence of triethylamine have been studied. It has been found that the corresponding (4+2) and/or (2+2) cycloadducts of benzoylsulfene and the anil were obtained, depending on the nature of the substituents, R, in the anils. The reaction of the chloride with benzylidene-n-propylamine in the absence of triethylamine gave only the (2+2) cycloadduct, while the (4+2) cycloadduct was exclusively obtained in the presence of triethylamine. The chloride reacted with dibenzylidenethylenediamine in the presence of triethylamine to give the corresponding bis(4+2) cycloadduct.
  • Tadashi Okuyama, Nobuhiro Asami, Takayuki Fueno
    1970 Volume 43 Issue 11 Pages 3549-3552
    Published: 1970
    Released: March 27, 2006
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    The cationic copolymerization between cis- and trans-styryl ethyl ethers in methylene chloride was investigated in the temperature range from −70 to 0°C with boron trifluoride etherate as catalyst. It was found that at lower temperatures the trans ether is more reactive than its cis isomer, although the relative reactivities are reversed at 0°C. Addition reactions of various acetals to cis- and trans-styryl ethyl ethers were carried out at 0°C with the same Lewis acid as catalyst. The relative cis-trans reactivities are largely dependent on the bulkiness of an attacking oxycarbonium ion. It was concluded that the cis isomer, which is electronically more reactive toward cations, is liable to suffer adverse steric effect, especially when the attacking carbonium ion is bulky.
  • Tadashi Okuyama, Nobuhiro Asami, Takayuki Fueno
    1970 Volume 43 Issue 11 Pages 3553-3556
    Published: 1970
    Released: March 27, 2006
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    Several ring-substituted derivatives of cis- and trans-styryl ethyl ethers were copolymerized with the unsubstituted trans ether in methylene chloride at −70°C with the use of boron trifluoride etherate as a catalyst. The ring substituents investigated include p-CH3O, p-CH3, m-CH3, p-Cl, and m-Cl. It was found that the effects of substituents on the polymerizability obey the Hammett ρσ relationship with reaction constants ρ=−2.4 and −2.0 for cis and trans isomers, respectively. The structure of the transition state of the cationic polymeization was discussed.
  • Noboru Sugiyama, Makoto Yamamoto, Choji Kashima
    1970 Volume 43 Issue 11 Pages 3556-3560
    Published: 1970
    Released: March 27, 2006
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    In the presence of three moles of potassium amide in liquid ammonia, the reactions of β-diketones with cinnamylidenaniline gave derivatives of 1-phenyl-2-styryl-2,3-dihydro-4-pyridone. By the catalytic hydrogenation of 6-methyl-1-phenyl-2-styryl-2,3-dihydro-4-pyridone, 6-methyl-2-phenethyl-1-phenyl-2,3-dihydro-4-pyridone was obtained. When β-diketones were treated with cinnamaldehyde azine, instead of cinnamylidenaniline, 1-cinnamylidenamino-2-styryl-2,3-dihydro-4-pyridones were produced; these were then catalytically hydrogenated to the corresponding 2-phenethyl-2,3-dihydro-4(1H)-pyridones, accompanied with 2-phenethyl-1-(3-phenylpropylamino)-2,3-dihydro-4-pyridones.
  • Shuzo Akiyama, Masazumi Nakagawa
    1970 Volume 43 Issue 11 Pages 3561-3566
    Published: 1970
    Released: March 27, 2006
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    A series of 9,9′-dianthrylpoly-ynes (II1–II6) were prepared, and their electronic spectra were measured. It was found that the novel linear relation between λmax and the square of the number of the triple bond (n2) which has been found in the spectra of 1,1′-dianthrylpoly-ynes (I1–I6) also held in the 9,9′-series.
  • Kazuhiro Nakasuji, Shuzo Akiyama, Kazuko Akashi, Masazumi Nakagawa
    1970 Volume 43 Issue 11 Pages 3567-3576
    Published: 1970
    Released: March 27, 2006
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    1,1′-Dinaphthylpoly-ynes (In, n=1–6) and 2,2′-dinaphthylpoly-ynes (IIn, n=1–6) were synthesized, and their electronic spectra were measured. The In-series gave an excellent agreement with the λmaxn1.5 relationship, and the IIn-series followed a straight line, λmaxn1.3. These relationships are different from those of 1,1′-dianthryl- and 9,9′-dianthrylpory-ynes, in which the plots of λmax versus n2 give excellent straight lines (Bull. Chem. Soc. Jap., 39, 2320 (1966); 40, 340 (1967)). The new linear relationships found in the dinaphthyl-series offer further evidence of the prominent effect of the terminal groups upon the electronic spectral properties of the conjugated poly-yne system.
  • Tetsuo Suami, Seiichiro Ogawa, Masaru Uchida
    1970 Volume 43 Issue 11 Pages 3577-3581
    Published: 1970
    Released: March 27, 2006
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    Seven inosamines (scyllo, chiro-1, myo-2, myo-4, allo-5, neo-1 and chiro-3) have been prepared from four bromodeoxyinositols [scyllo, chiro-1, allo-5 and neo-1). When bromodeoxyinositols were treated with sodium azide in boiling aqueous 2-methoxyethanol or dimethylformamide, followed by acetylation, pentaacetyl azidodeoxyinositols were obtained in 60–80% yield. On catalytic hydrogenation using Adams’ platinum oxide, the azido compounds yielded hexaacetyl inosamines in good yields. Proton magnetic resonance (PMR) spectra of acetyl azidodeoxyinositols have been studied.
  • Kinko Koyano, Hiroshi Suzuki, Yuji Mori, Ikuzo Tanaka
    1970 Volume 43 Issue 11 Pages 3582-3587
    Published: 1970
    Released: March 27, 2006
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    Fifteen nitrones, N-butylidenecyclohexylamine N-oxide, N-benzylidenemethylamine N-oxide, N-diphenylmethylenemethylamine N-oxide, N-benzylidenaniline N-oxide, and its derivatives, were irradiated with light in solution, each at its longest-wavelength absorption band. Each nitrone isomerized to the corresponding oxazirane. The quantum yield of this photo-rearrangement, Φ, was measured. For each nitrone, the value of Φ is larger in cyclohexane solution than in ethanol solution. In the series of N-benzylidenaniline N-oxide and its para-substituted derivatives, the substituent lowers Φ, and the more electron-donating or the more electron-withdrawing the substituent is, the smaller is Φ. These facts are explained on the basis of a hypothesis that π should increase with the change in the π-bond order between the carbon and oxygen atoms of the nitrone group upon the lowest-energy electron excitation, ΔPC,O, calculated by the simple MO method.
  • Masayuki Yoshida, Akira Matsumoto, Osamu Simamura
    1970 Volume 43 Issue 11 Pages 3587-3590
    Published: 1970
    Released: March 27, 2006
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    2-Aryl-5-phenyltriazolo[4,5-d]triazoles and related compounds, a new heteroaromatic system, have been prepared from 4,5-diamino-2-phenyl-1,2,3-triazole. The meso-ionic character of the new ring system is discussed on the basis of proton NMR shifts.
  • Toshio Nakata, Katsumi Tokumaru, Osamu Simamura
    1970 Volume 43 Issue 11 Pages 3590-3593
    Published: 1970
    Released: March 27, 2006
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    Thermal decomposition of diisopropyl peroxydicarbonate in benzene was carried out at several temperatures ranging from 40 to 70°C under an atmosphere of nitrogen, air or oxygen; the presence of oxygen caused the production of isopropyl phenyl carbonate. For this aromatic isopropyloxycarbonyloxylation induced by oxygen, a mechanism is proposed, which involves reversible addition of an isopropyloxycarbonyloxy radical to an aromatic nucleus to give a cyclohexadienyl intermediate, followed by oxidation with oxygen to produce the carbonate ester. The reaction in a mixture of benzene and hexadeuteriobenzene showed isotope effects for the formation of the ester, kHkD=2.1–2.3, thus supporting the reversibility of the addition step of the isopropyloxycarbonyloxy radical to benzene.
  • Yoko Naya, Munio Kotake
    1970 Volume 43 Issue 11 Pages 3594-3596
    Published: 1970
    Released: March 27, 2006
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    The steam-volatile constituents of Humulus japonicus Sieb. et Zucc. have been studied, and 50 compounds of the oil have been identified mainly by means of the temperature-programmed capillary GLC mass-spectra method. Beside the previously-reported principal components of hops (α-humulene, caryophyllene, α-copaene, α- and β-selinenes, γ-cadinene, caryophyllene-oxide, and humulene-epoxide-II), benzyl alcohol and phenethyl alcohol were found in high concentrations, whereas the myrcene was negligible. The proportion of the main compound, humulene, to the next highest one, caryophyllene, was approximately in the ratio of two to one, as in the essential oil of H. lupulus. As far as the chemical composition of the essential oils is concerned, H. japonicus seems to be related rather more closely to H. lupulus than to H. cordifolius.
  • Akira Misono, Yasuzo Uchida, Kunikazu Yamada
    1970 Volume 43 Issue 11 Pages 3597-3601
    Published: 1970
    Released: March 27, 2006
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    The high resolution NMR spectra of vinyl chloride-ethylene copolymers obtained by trialkylboron catalyst have been analyzed. The copolymer composition could be determined from the resonance peak area, and the monomer reactivity ratios thus obtained were in good consistency with those determined from the results of elementary analysis. The fine structure of the copolymers have been elucidated in terms of the run number concept, and the distribution of dyads as well as the average sequence lengths of the monomer unit have been determined. It was found that the observed values fitted theoretical values, indicating that a terminal model holds in this copolymerization.
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