Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 42 , Issue 5
Showing 1-50 articles out of 77 articles from the selected issue
  • Seiichi Kondo, Masa-aki Muroya
    1969 Volume 42 Issue 5 Pages 1165-1170
    Published: 1969
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The effect of water adsorption and heat treatment at various temperatures between 200 and 1100°C on the dielectric dispersions of silica gel was measured in the frequency range from 50 to 3×106 Hz and 9.81 GHz and in the temperature range from −196°C to 180°C. Two anomalous dispersions (Dispersion I and II) and one anomaly (Anomaly III) were found. The mechanisms of those anomalies were discussed in relation to some physical properties and silica crystal structures. Dispersion I, having activation energy ΔE equal to 11 to 14 kcal/mol, can be ascribed to the monomolecular layer of adsorbed water. Dispersion II, with activation energy of about 5 to 7 kcal/mol, can be attributed to proton diffusion through hydrogen-bond chain of surface silanol groups. Anomaly III, having activation energy of about 3 kcal/mol, may be assigned to dipolar rotation of free silanol.
  • S. P. Jain, S. N. Srivastava
    1969 Volume 42 Issue 5 Pages 1171-1178
    Published: 1969
    Released: March 27, 2006
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    Mechanism of emulsification with special reference to ferric hydroxide as emulsifier has been studied. The sol of ferric hydroxide having maximum possible stability has been prepared. Its particle size as determined by electron microscope is of 63 Å radius. The stability of the sol in presence of different amounts of electrolytes of different valencies has been studied by measuring its zeta potentials in terms of interaction energy curves. By using these different stages of partially flocculated ferric hydroxide sol as emulsifier the emulsions of toluene in water were prepared and their relative stabilities assessed by adding various electrolytes. Then the stability of the emulsions formed has been studied by the measurement of zeta potentials micro-electrophoretically in the light of the D.V.O. theory. The size of the emulsion globules as determined microphotographically is 1.1μ radius. The pH and interfacial tension measurements have also been carried out. From interfacial tensions between the disperse phase and the dispersion medium at different amounts of electrolytes, the surface charge of the emulsions has been deduced which is found to be in good agreement with the electrophoretic results. Finally a correlation has been sought between the stability of the emulsions and the corresponding partially flocculated sols used in emulsification.
  • J. M. Jackman, George Y. Sarkis
    1969 Volume 42 Issue 5 Pages 1179-1186
    Published: 1969
    Released: March 27, 2006
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    The magnetic shielding of nuclei due to distant chemical groups may be calculated from the knowledge of the magnetic anisotropy of the bonds in these groups. The reverse procedure, namely, the calculation of the magnetic anisotropy of bonds from NMR relative chemical shifts has been employed here to estimate the magnetic anisotropy of −C≡C, −C≡N, and −N≡C triple bonds. The paramagnetic contribution to the shielding of the acetylenic proton was estimated from the calculated value of ΔχC≡C, and from the known geometry of the molecule. The value thus obtained is compared with that calculated by quantum mechanical methods.
  • Osamu Kikuchi
    1969 Volume 42 Issue 5 Pages 1187-1191
    Published: 1969
    Released: March 27, 2006
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    Quantitative discussions of the ESR spectra of aliphatic nitric oxide radicals have been undertaken on the basis of the molecular orbitals of all-valence-electrons, which were evaluated by the approximate SCF method with the CNDO/2 approximation. The spin density on the methyl proton in the dimethyl nitric oxide radical is proportional to cos2θ, where θ is the angle between the nitrogen 2pz orbital and the plane containing the C–N and the G–H bonds; the small hyperfine splitting constants of β-protons appearing in some substituted nitric oxide radicals are understood as resulting from the sterically-restricted conformations of substituted groups. The deviation of the g factor of aliphatic nitric oxide from the free spin comes from the large spin densities localized on the nitrogen and the oxygen atoms, and the small excitation energy, from the nonbonding orbital of the oxygen to the odd π-orbital. The electronic structures and g factors of some other radicals are compared to those of aliphatic nitric oxide radicals.
  • Kenzo Fukuda, Takaharu Onishi, Kenzi Tamaru
    1969 Volume 42 Issue 5 Pages 1192-1196
    Published: 1969
    Released: March 27, 2006
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    The mechanism of the decomposition of formic acid over reduced silver catalyst has been studied by means of the adsorption measurement during surface catalysis. It was found that the decomposition of formic acid on the silver catalyst at 100°C was first order at lower pressures of formic acid, while at medium pressures it was zero order, the reaction rate being independent of the pressures of ambient formic acid; in the first region the amount of adsorbed formic acid was proportional to the pressure of formic acid, and in the second region it was constant, independent of the pressure of formic acid in the ambient gas. The second region corresponds to “saturation” in an ordinary sense. At pressures of formic acid higher than that in the “saturation” region the amount of adsorbed formic acid increases again linearly with the pressure of formic acid. The linear relation between the reaction rate and the amount of formic acid adsorbed during the reaction was observed over the whole range of the pressure of formic acid studied. It is accordingly concluded that a surface unimolecular reaction in terms of the adsorbed formic acid is the ratedetermining step. The exchange reaction of surface formic acid with those in the ambient gas was studied and it was demonstrated all the formic acid in the adsorbed layer accordingly participated in the exchange reaction. The numbers of surface silver atoms occupied by one molecule of adsorbed formic acid at the saturation points at various temperatures are estimated from the number of surface silver atoms and the amount of formic acid adsorbed at the zero-order kinetics. The number of surface silver atoms occupied by one molecule of adsorbed formic acid increases linearly with temperature.
  • Tadamasa Shida, Akira Kira
    1969 Volume 42 Issue 5 Pages 1197-1201
    Published: 1969
    Released: March 27, 2006
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    Dilute solutions of acridine in ethers and amines were frozen at −196°C to a glassy solid and were γ-irradiated. Electrons ejected by ionization are effectively scavenged by acridine to produce acridine anions which are the sole species having an electronic absorption band in the visible region. In alcohol and ester matrices the anion abstracts a proton from the matrix molecule even at −196°C and yields a semiquinone radical equivalent to the species formed by H-atom abstraction at the 9-position of acridan (dihydroacridine). Acridan in γ-irradiated butyl chloride matrix forms acridan cation which has a characteristic absorption band at 500–750 mμ. Detachment of a proton from the acridan cation produces another semiquinone radical identifiable with the species formed by H-atom abstraction at the 10-position of acridan. Both radicals have a similar yet clearly distinguishable absorption band in the visible region.
  • Takashi Tahara, Iwao Satake, Ryohei Matuura
    1969 Volume 42 Issue 5 Pages 1201-1205
    Published: 1969
    Released: March 27, 2006
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    The disodium monoalkyl phosphate with n-dodecyl, n-tetradecyl and n-hexadecyl radical was synthesized, and pNa and light scattering studies were performed on the micellar properties of these surfactants in aqueous solutions. The critical micelle concentrations (CMC) of these salt solutions were confirmed to be considerably higher than those of ordinary 1–1 type ionic surfactants with the same alkyl chain length. The degree of dissociation of the micelle was, however, found to be not so different from that of corresponding sodium alkyl sulfate. The fact that these salts have comparatively large aggregation number reflects one of the characteristic features of alkyl phosphate anion which has two dissociable groups.
  • Keishiro Shirahama, Makoto Hayashi, Ryohei Matuura
    1969 Volume 42 Issue 5 Pages 1206-1212
    Published: 1969
    Released: March 27, 2006
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    The solubilities and critical micelle concentrations (CMC) of potassium dodecyl sulfate (KDS) and hexadecyl sulfate (KHS) were measured in methanol-, ethanol-, 1-propanol-, ethylene glycol-, 1,2-propanediol-, and glycerol-water mixed solvents over the temperature range from 0 to 40°C. It was found that the higher the hydroxy group density in the solvent, the less the effects on both the solubility and the CMC, and that the presence of an alkyl group in the solvent causes a greater temperature-dependence in the solubility. The solvent effects on the CMC and on the single-ion dispersion were discussed separately. An effect of a net-work structure formed between the hydroxy compound and water on the solubility is suggested. Solvent effects on the alkyl group and the ionic group of a surfactant molecule were separated by considering the difference between the standard free-energy change for the solution process of KHS and that of KDS. The effects on the Krafft point were also discussed in term of the above suggestions.
  • Noriko Ohigashi, Hiroo Inokuchi
    1969 Volume 42 Issue 5 Pages 1212-1216
    Published: 1969
    Released: March 27, 2006
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    The static magnetic susceptibilities of poly crystalline samples of 1,1-bis(p-chlorophenyl)-2-picrylhydrazyl (Cl-DPPH), 1,1-bis(p-bromophenyl)-2-picrylhydrazyl (Br-DPPH), and 1,1-bis (p-methoxyphenyl)-2-picrylhydrazyl (CH3O-DPPH) were measured in the temperature range from 10°K to 300°K. These three substances showed strong paramagnetism comparable to that of DPPH, having relatively weak interaction energies between their unpaired electrons. Of these, the paramagnetic susceptibility of CH3O-DPPH was analysed on the basis of the singlet-triplet model with the energy separation of 2J/k=33.8°K.
  • Fumikatsu Tokiwa, Kenji Ohki
    1969 Volume 42 Issue 5 Pages 1216-1219
    Published: 1969
    Released: March 27, 2006
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    The electrophoretic properties of the micelle of sodium dodecyltrioxyethylene sulfate have been studied in the presence of various types of inorganic z+-z electrolytes and in the presence of organic electrolytes (RNH3Cl and RCOONa) of various sizes. The effect of the type of electrolytes on the zeta potential of the micelle, ζ, is similar in tendency to the effect to be expected on the basis of the Gouy-Chapman equation for spherical colloid particles. The valence of counterions has a considerable effect on ζ, but that of the co-ions has only a slight effect. With respect to the size of ions, counter-ions (RNH+) appreciably influence the potential of the micelle, whereas co-ions (RCOO) influence the potential almost not at all. The value of ζ slightly increases, and then steeply decreases, with an increase in the size of the cations through a maximum value.
  • Yasukatsu Tamai, Yoshihiro Momose
    1969 Volume 42 Issue 5 Pages 1219-1222
    Published: 1969
    Released: March 27, 2006
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    The exo-electron glow curves up to about 250°C were measured for the sandblasted steel specimens, which had been kept in air for 2 min 30 sec, 2 hr 30 min or 13 hr after the sandblast. It was found that the plots of the integrated total counts against the keeping time in doublelogarithmic scales gave a straight line with negative slope and that the emission peak moved to higher temperatures and at the same time the emission intensity decreased with the keeping time. It was also found that at the higher heating rate the peak intensity became larger and the peak temperature became higher than at the lower heating rate and that the remaining counts above a given temperature in the glow curve was linearly related with the temperature in semi-logarithmic scales, regardless of the heating rate. Comparing the behavior of exo-electron emission with that of the thermoluminescence of phosphors, it is supposed that electron traps are distributed on or in the deformed solid surface.
  • Masae Nemoto, Hiroshi Kokubun, Masao Koizumi
    1969 Volume 42 Issue 5 Pages 1223-1230
    Published: 1969
    Released: March 27, 2006
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    Intersystem crossing probability, \varphiSTA for fluorescein, eosine, erythrosine, methylene blue and thionine in ethanol (only for fluorescein, 30 vol% alkaline aqueous ethanol solution), has been determined by comparing the quantum yield of the direct (Φ) and sensitized photoreduction (Φs), on the basis of the following relations,
    Φ=\varphiSTAβ Φs=\varphiSTDγβ
    where β is the fraction of triplet dye molecules that are reduced eventually, \varphiSTA and \varphiSTD are respectively for acceptor (dye) and donor (sensitizer) and γ is the energy transfer efficiency, which was assumed as 1. ATU was used as a reducing agent. 1,2,5,6-dibenzanthracene, triphenylene, anthracene and β-acetonaphthone were used as sensitizers. It has been confirmed that the above relations and assumption hold generally. Different sensitizers usually gave nearly the same \varphiSTA values (with the exception of thionine-anthracene. β-Acetonaphthone gave in general somewhat smaller values). The most probable \varphiSTA values obtained are; fluorescein (0.007), eosine 0.43±0.04, erythrosine 1.1±0.06, methylene blue 0.52±0.03, thionine 0.62±0.03. The values for xanthene dyes agree moderately well with the ones reported by Porter et al. for the aqueous solution of pH=9, fluorescein 0.05, eosine 0.71, erythrosine 1.07. Using the above \varphiSTA values, the ratio of the deactivation and genuine reaction between triplet dye and ATU has been evaluated. The ratio increases in the order, fluorescein<eosine<erythrosine, thionine<methylene blue.
  • Yoshiharu Usui, Chieko Iwanaga, Masao Koizumi
    1969 Volume 42 Issue 5 Pages 1231-1239
    Published: 1969
    Released: March 27, 2006
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    Under experimental conditions in which the interaction between triplet dye and oxygen is an initiating process (D–O mechanism), the photosensitized oxidation of leucofluorescein in the aqueous solution (reaction (1)) has been found to decrease in rate with the increasing oxygen concentration and that the magnitude of the retarding effect of oxygen is almost the same independent of sensitizing dye. This is in sharp contrast to the kinetic feature of the oxidative photobleaching of dye (reaction (2)), where the rate becomes constant beyond a certain small oxygen concentration. On the basis of these findings, it has been proposed that in reaction (1), 1O2 plays a dominant role and it is deactivated by process 1O2+3O2→23O2. As to reaction (2), strong evidence has been presented for the view that the interaction of triplet dye and oxygen in the aqueous solution produces a rather stable D+···O2 of which only a small portion decomposes irreversibly. The principal evidence is as follows; 1) the free half-oxidized dye (produced by the reaction between triplet dye and [Co(Ox)3]3− was found to oxidize FH2 with a high rate and its decay was found to be accelerated by the addition of FH2; 2) the decay of the half-oxidized species (first order decay!) produced in the aerated aqueous solution, on the other hand, was not affected by FH2 under otherwise similar conditions as in (1).
  • Hirotaka Shimanouchi, Norio Saito, Yoshio Sasada
    1969 Volume 42 Issue 5 Pages 1239-1247
    Published: 1969
    Released: March 27, 2006
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    Crystals of N-(p-bromophenyl)-α-D-ribopyranosylamine 2,4-phenylboronate, C17H17O4NBBr, are monoclinic, with two molecules in a unit cell of the dimensions, a=12.98, b=10.80, c=6.34Å, and β=99.4°, and with the space group of P21. The intensity data were collected by a photographic method and the structure was solved by the heavy atom method. The final R factor is 0.100. The absolute configuration was also determined.
  • Teijiro Yonezawa, Isao Morishima, Mutsuo Fujii, Hiroshi Kato
    1969 Volume 42 Issue 5 Pages 1248-1256
    Published: 1969
    Released: March 27, 2006
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    An attempt has been made to explain the experimental trend of H–H and 13C–H nuclear spin coupling constants for CH3X, (CH2)2X, and CH2=CHX systems on the basis of the Pople and Santry expression for the contact term. The calculated magnitudes of the coupling constants are parallel with the observed values, but are uniformly lower by a factor of between 1.5 and 2. The variation in the calculated coupling constants with the electronegativity (Ex) of the substituent, X, follows the well-acknowledged observed tendency for directly-bonded 13C–H, geminal H–H, and vicinal cis and trans H–H coupling constants. Theoretical calculations also predict the Ex dependency of the directly-bonded 13C–H coupling constants for two geminal C–H bonds in the 13CH2=CHX fragment. The difference between two geminal 13C-C-H coupling constants in the CH2=13CHX system is also obtained by calculation. Discussions of the factors which dominate the couplings are also presented.
  • Hideyuki Hao, Hiroshi Fujimoto, Kenichi Fukui
    1969 Volume 42 Issue 5 Pages 1256-1263
    Published: 1969
    Released: March 27, 2006
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    The change in the electronic state in the course of the E2 reaction of ethyl chloride was followed by means of the extended Hückel calculation. A model is adopted in which the nucleophilic reagent approaches the trans-β-hydrogen atom. The valence-inactive population of the trans-β-hydrogen atom in the lowest unoccupied (LU) molecular orbital (MO) was employed as a theoretical reactivity index. The theoretical conclusion derived was consistent with the experimental results.
  • Teruhiko Ogata, Kunio Kozima
    1969 Volume 42 Issue 5 Pages 1263-1265
    Published: 1969
    Released: March 27, 2006
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    The microwave spectrum of cyclohexene has been investigated in the frequency region from 7.3 to 27 Gc/sec with a conventional Stark modulation spectrometer, and the spectrum in the ground vibrational state has been assigned. The dipole moment lies entirely along the b-principal axis; its value, as obtained from the Stark displacements, is 0.332±0.012D. From the rotational constants and the orientation of the dipole moment, it can be concluded that the equilibrium conformation is a “half-chair” form. Its most probable structure has been determined.
  • Tetsuo Takaishi
    1969 Volume 42 Issue 5 Pages 1266-1271
    Published: 1969
    Released: March 27, 2006
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    The conditions for the applicability of the McKay law were studied. It was concluded that the first order kinetics no longer holds when the concentrations of intermediates cannot be disregarded when compared with those of reactants and products and when the rate determining step cannot be specified. Some reactions were illustrated in which McKay’s law cannot be applied.
  • Takasuke Matsuo, Masayasu Sugisaki, Hiroshi Suga, Syûzô Se ...
    1969 Volume 42 Issue 5 Pages 1271-1277
    Published: 1969
    Released: March 27, 2006
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    The heat capacities of TlCN crystal were measured from 15 to 300°K with an adiabatic calorimeter. Three regions of anomalously high heat capacity were discovered. Thermodynamic functions of the crystal were calculated by the graphical integration of the heat capacity data. 205Tl nuclear magnetic resonance was observed as functions of temperature and applied static magnetic field. Their second moment values could be interpreted in terms of the anisotropic chemical shift tensor.
  • Tsunenobu Shigematsu, Masakazu Matsui, Kei Utsunomiya
    1969 Volume 42 Issue 5 Pages 1278-1281
    Published: 1969
    Released: March 27, 2006
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    The gas chromatographic behavior of Sc, Y, and rare earth chelates of a new β-diketone, pivaroyltrifluoroacetone (PTA), was investigated. PTA was synthesized by a Claisen condensation from pinacolin and ethyltrifluoroacetone. Sc, Y, Nd, Sm, Eu, Gd, Tb, Dy, Er, Yb, and Lu PTA chelates were prepared. Their elemental analyses and infrared spectra indicated that they were anhydrous tris chelates, and the TGA curves of the chelates proved their good volatile characteristics, showing approximately a 100% weight loss. Gas chromatograms of all the chelates and of mixtures of Sc, Y, and several rare earth chelates were obtained. Some relationships were observed between the retention time, the volatilization temperature, and the ionic radius of the central metal: With the decrease in the ionic radius, the retention time of the chelate decreased and the volatilization temperature became lower.
  • Takayoshi Yoshimori, Syuiti Ishiwari
    1969 Volume 42 Issue 5 Pages 1282-1285
    Published: 1969
    Released: March 27, 2006
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    Sodium amide was used to convert a microamount of water into ammonia in a carrier gas. The ammonia was then titrated with coulometrically generated hypobromite ions. The reaction between water and sodium amide was completed stoichiometrically, and the reaction rate was considerably promoted by heating sodium amide at 80°C. The sample hydrogen was oxidized with copper(II) oxide at 800°C, and the water thus produced was determined by this method. 0.096–0.665 ml (8.6–59.8 μg) of hydrogen and 0.055–0.465 mg of water in barium chloride crystals were determined within errors of 3.6% and 3.0% respectively. The water adsorbed on the surfaces of the weights was also determined by this method at various humidities.
  • Haruko Ito, Junnosuke Fujita, Kazuo Saito
    1969 Volume 42 Issue 5 Pages 1286-1291
    Published: 1969
    Released: March 27, 2006
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    Absorption (AB) and circular dichroism (CD) spectra of trans-[MX2(l-pn)2]n+ (where M=RhIII, PdIV- and PtIV-, and X=Cl and Br) have been discussed by comparing them with those of cobalt (III) complexes which had been studied extensively. A positive CD peak was observed at around the so called Ia band region of all the complexes studied except for trans-[PtBr2(l-pn)2]2+. A negative CD peak of this complex ion at 26000 cm−1 was assigned to be a split component of the Ia band. The AB peaks at 38000, 28600 and 31100 cm−1 for trans-[PtCl2(l-pn)2]2+, trans-[PdCl2(l-pn)2]2+ and trans-[PtBr2(l-pn)2]2+ respectively were assigned to pπ→dz2 charge transfer transition. An ion association band was observed for trans-[PtBr2(l-pn)2]Br2 in 1N hydrobromic acid.
  • Ikuko Akaza, Toshiyasu Kiba, Minoru Taba
    1969 Volume 42 Issue 5 Pages 1291-1296
    Published: 1969
    Released: March 27, 2006
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    The separation of hexacyanoferrate(II) and (III) ions with a TBP-HCl extraction system has been carried out by reversed-phase partition column chromatography. TBP adsorbed on Kel-F powder was used as the stationary phase in the column. Elution was performed with hydrochloric acid of various concentrations and with water, both having been saturated with TBP. The actual separation of hexacyanoferrate(II) and (III) ions from each other was successfully achieved, even in a large volume of a sample solution, by carrying out the elution with 3N HCl. The dependencies of the distribution ratio on the acidity of the solution and on the concentration of TBP in the stationary phase were examined on the basis of the elution curves under various conditions. The liquid-liquid batch extraction was also carried out under the same conditions; it was found an identical relation of distribution between the two phases held in both column and batch extractions. The principal extracted species might be assumed to be a large ion-pair hydrated and solvated.
  • Kazuko Hamada, Hideo Ueda, Yasuo Nakao, Akitsugu Nakahara
    1969 Volume 42 Issue 5 Pages 1297-1300
    Published: 1969
    Released: March 27, 2006
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    The reactions of bis(salicylaldehydato)copper(II) in acidic, neutral and basic media with glycinamide, glycinester, glycylglycinamide and glycylglycinester have been systematically investigated. The reaction products have, in all cases, been isolated as crystals and characterized. As a result of this investigation, six new copper(II) chelates of Schiff bases derived from salicylaldehyde and glycine- or glycylglycine-amide have been obtained. The interrelation between those chelates has also been disclosed.
  • Yuki Fujii, Eishin Kyuno, Ryokichi Tsuchiya
    1969 Volume 42 Issue 5 Pages 1301-1304
    Published: 1969
    Released: March 27, 2006
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    The following three mixed chromium(III) complexes containing acetylacetone, which had a charge of from −1 to +1, were prepared: NH4[Cr(acac)(ata)]·H2O, [Cr(acac)(edda)]·2H2O and [Cr(acac)(edma)(H2O)]Cl·H2O. The halogenations at γ-position of the acetylacetonate ring were attempted in these three mixed complexes with NCS, NBS and ICl respectively in methanol and in acetic acid solutions, where NCS, NBS and ICl are abbreviated forms of N-chlorosuccinimide, N-bromosuccinimide and iodine monochloride, respectively. From an inspection of UV-spectra of the above halogenation reaction mixtures, all the three mixed complexes were confirmed to be halogenated at the γ-position of the acetylacetonate ring. Of these complexes, NH4[Cr(acac-Cl)(ata)]·\frac12H2O and [Cr(acac-Br)(edda)] were isolated as crystals from the reaction mixtures. IR-spectra measurement was also used to certify the halogen-substitution at γ-position in the above two compounds.
  • Takao Umegaki, Taijiro Okabe, Keiichi Omori
    1969 Volume 42 Issue 5 Pages 1304-1307
    Published: 1969
    Released: March 27, 2006
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    Crystal growth of the phosphate coating on steel and pure iron was investigated by microscopic observation and X-ray diffraction. β-Hopeite was recognized as a main constituent of the phosphate coating. From the experimental results obtained in this investigation and the crystal structure of β-hopeite proposed by Gamidov and Galovachev (Dokl. Akad. Nank, SSSR, 150, 2, 381, (1963)), it was concluded that the bonding of the (010) plane of β-hopeite to the (100) plane of iron is most favorable for atomic arrangement of the phosphate coating.
  • Tadashi Sasaki, Fujinao Matsunaga
    1969 Volume 42 Issue 5 Pages 1308-1316
    Published: 1969
    Released: March 27, 2006
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    Bis(dimethylglyoximato)cobalt(III) complexes with the general formula: [CoX(DH)2BA] (X: CN, NO2, SeCN, SCN, Br. D: dianion of dimethylglyoxime. BA: such biologically interesting bases as imidazole, benzimidazole, 5,6-dimethylbenzimidazole, pyridine, γ-picoline, 4-vinylpyridine, nicotinic acid, isoquinoline, 5-amino-4-imidazolecarboxamide, and 6-aminopurine) were prepared from dimethylglyoxime, the base, and an adequate cobalt (III) salt. The treatment of [CoCN(DH)2Imd] (Imd: imidazole) with boron trifluoride etherate afforded [Co(CNBF3)(DBF2)2Imd] in an 86% yield. The reduction of [CoCl(DH2)Imd] with sodium borohydride gave a labile [Co(I)H(DH)2Imd], which was directly converted with phenylacetylene into a stable [Co(III)(C6H5CH=CH)(DH2)Imd] in a 60% yield and into [Co(DH)2Imd]·H2O in a 30% yield. These products were structurally elucidated on the basis of their spectral data.
  • Teruzo Asahara, Manabu Sen\={o}, Takeshi Arai
    1969 Volume 42 Issue 5 Pages 1316-1321
    Published: 1969
    Released: March 27, 2006
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    The electrolytic reductive dimerization of acrylonitrile was investigated extensively especially in order to obtain some mechanistic information. The essential point of this reaction exists in the selective formation of adiponitrile under relatively wide conditions and this cannot be explained by a normal kinetic treatment based on the reaction scheme which has been accepted as probable. The heterogenuity in acrylonitrile concentration in the reaction system is assumed and the kinetic formulas are modified. This treatment explains the experimental results very satisfactorily. In order to confirm this mechanistic scheme, the effects of temperature, pH and solvents on the yield of reaction products were examined. All the results are consistent with the proposed mechanism.
  • Shinichi Motoki, Tadao Sato
    1969 Volume 42 Issue 5 Pages 1322-1324
    Published: 1969
    Released: March 27, 2006
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    Ketene dimer reacted with mercaptan to give acetothiolacetate (I) in the presence of triethylamine. The ester I underwent a thermal condensation to give dehydroacetic acid (III), with the liberation of mercaptan, merely upon heating, and the reaction was effectively promoted in the presence of triethylamine. The ester I reacted with alkyl halide and acyl halide in dioxane to give α-alkyl and α-acylacetothiolacetate (II) respectively. Ethyl acetothiolacetate, ethyl α-methyl-acetothiolacetate, and ethyl α-acetylacetothiolacetate reacted with mercuric oxide at a low temperature to give diacetylacetone (VI), methyl ethyl ketone, and dehydroacetic acid (III) respectively.
  • Norio Kunieda, Shigeru Oae
    1969 Volume 42 Issue 5 Pages 1324-1328
    Published: 1969
    Released: March 27, 2006
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    When 18O-labeled and optically active sulfoxides are dissolved in a concentrated sulfuric acid, one observes the concurrent oxygen exchange and racemization reactions of the sulfoxides, and these reactions were found to proceed through the SN1-like path (S. Oae et al., Bull. Chem. Soc. Japan, 38, 546 (1965); 41, 696 (1968)). We have found that the concurrent oxygen exchangeand racemization reactions also take place even in less concentrated sulfuric acid at somewhat higher temperature, i. e. 70% sulfuric acid at 30°C, and proceed through a different mechanistic route, very likely an SN2-like path. Kinetic investigation on these reactions in sulfuric acid of various concentrations (66.5–96.3%) suggests there is a gradual change of mechanism of the reaction, i. e. from SN2 type in 66.5% to SN1 type in 96.3% with the increase of the concentration of sulfuric acid.
  • Hajime Kanatomi, Ichiro Murase
    1969 Volume 42 Issue 5 Pages 1329-1332
    Published: 1969
    Released: March 27, 2006
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    The reactions of salicylamine with α-dicarbonyl compounds were examined in the hope of obtaining 2,2′-bibenzoxazine derivatives I or Schiff bases II as two-to-one condensation products; however, salicylidenesalicylamine was isolated in every case. It was found that the reaction proceeded through transamination, followed by trans-Schiffization between salicylamine and α-dicarbonyl compounds. The mechanism and the conditions under which the reactions take place were investigated.
  • Rume Sakai, Shoichi Ikeda, Toshizo Isemura
    1969 Volume 42 Issue 5 Pages 1332-1336
    Published: 1969
    Released: March 27, 2006
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    The equilibrium conformations of three copolymers of L-proline with β-benzyl-L-glutamate were studied in 1,2-dichloroethane, m-cresol, and dichloroacetic acid by measuring the optical rotatory dispersion and the infrared absorption spectra. In m-cresol and dichloroacetic acid, the proline residues take the trans-configuration. In m-cresol their incorporation into copolymers destroys the right-handed-α-helical conformation of glutamate residues. In 1,2-dichloroethane, the proline residues assume the cis-configuration if the sequence of proline residues is long enough. If it is short, they are in the trans-configuration. The poly-L-proline-I-helix can never coexist with the α-helix.
  • Rume Sakai, Toshizo Isemura
    1969 Volume 42 Issue 5 Pages 1337-1342
    Published: 1969
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Three copolymers of L-proline and L-glutamic acid were synthesized, and their equilibrium conformation in an aqueous solution was studied in relation to their composition. The molar ratios of the proline to the glutamic acid residues in the copolymers were about 1:3, 1:1, and 8:1. All the copolymers were soluble in water, as were poly-α,L-glutamic acid and poly-L-proline II. The conformational change was caused by the pH effect on proline-poor copolymers. Evidence was obtained for the possibility of the absence of such a helix as a right-handed poly-L-proline-I-helix in the copolymers examined. The conformation of Copoly-8:1 was not affected by the pH and was identified as the poly-L-proline-II-helix.
  • Kyoji Kaeriyama
    1969 Volume 42 Issue 5 Pages 1342-1344
    Published: 1969
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Styrene was polymerized in dimethyl sulfoxide by alcohol-ceric salt containing lauryl sulfuric ions. The rate of polymerization increased with the amount of ethyl alcohol added. A deuterium isotope effect was observed when tetradeuteromethyl alcohol was used as an initiator. Accordingly, the generation of radicals by the elimination of the hydrogen atom from the alcohol molecule was concluded. When styrene was polymerized in the presence of cellulose, graft copolymer was obtained. The grafting efficiency amounted to about 70%.
  • Tsunehiko Kuwamura, Hideo Takahashi
    1969 Volume 42 Issue 5 Pages 1345-1350
    Published: 1969
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    When alkyl glycidyl ethers derived from epichlorohydrin and alcohols were treated with sodium cyanide, the corresponding γ-alkoxy-β-hydroxybutyronitriles (I) were obtained. The hydrolysis of I with aqueous alkali metal hydroxide, followed by acidification and distillation, gave γ-alkoxy-γ-butyrolactones (II). The structure of II was confirmed by chemical and physical means. The reaction paths of I to II were also studied.
  • Masatomo Nojima, Niichiro Tokura
    1969 Volume 42 Issue 5 Pages 1351-1353
    Published: 1969
    Released: March 27, 2006
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    The isomerizations of bicyclo[5.4.0]undecene-(1,7) (IV), spiro[5.5]undecene-1 (V), and 1-cyclopentylcyclohexene (VI) were examined with equivalent amounts of perchloric acid in acetic acid or in ethanol at 75°C. In acetic acid, IV, V, and VI all rearranged to form spiro[5.5]-undecan-1-yl acetate (VII) and spiro[5.5]undecan-2-yl acetate (VIII), together with the three olefins IV, V, and VI. No rearranged product has been obtained by the same procedure in ethanol.
  • Noboru Sugiyama, Hiroshi Kataoka, Choji Kashima, Kazutoshi Yamada
    1969 Volume 42 Issue 5 Pages 1353-1356
    Published: 1969
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The product of the irradiation of trans-β-benzoylacrylic acid (1) in methanol was proved to be α-methoxy-β-benzoylpropionic acid (2), whose methyl ester was identified with an authentic material. On the other hand, the product of the irradiation of methyl trans-β-benzoylacrylate (5) was the cis-isomer. The photoreaction of 1 in various solvents, including EtOH, iso-PrOH, t-BuOH, ether, and AcOH, was examined from the standpoints of the cis-trans isomerization and alcohol addition. The rate of the photoreaction of 1 in methanol was determined, and a reasonable mechanism for the over-all reaction was proposed.
  • Noboru Sugiyama, Makoto Yamamoto, Choji Kashima
    1969 Volume 42 Issue 5 Pages 1357-1359
    Published: 1969
    Released: March 27, 2006
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    The condensation of β-diketones, benzoylacetone (II), acetylacetone (III), or 6-phenyl-2,4-hexanedione (IV) with benzylidenaniline (I), in the presence of three moles of potassium amide in liquid ammonia, was found to give a dihydropyridone or an aminodiketone. Thus, the condensation of II with I afforded aminodiketone, 1-anilino-1,5-diphenyl-3,5-pentanedione (V), which cyclized to 2,3-dihydro-1,2,6-triphenyl-4-pyridone (IX) upon being treated with sulfuric acid. The condensation of III with I gave 2,3-dihydro-1,2-diphenyl-6-methyl-4-pyridone (X) without any treatment with sulfuric acid. IV and I gave 2,3-dihydro-1,2-diphenyl-6-phenethyl-4-pyridone (XI) as the main product, with 3-benzyl-2,3-dihydro-1,2-diphenyl-6-methyl-4-pyridone (XII) as a by-product.
  • Akira Watanabe, Akio Ishizawa, Masao Kosaka, Ry\={o}z\={o} Got\={o}
    1969 Volume 42 Issue 5 Pages 1360-1363
    Published: 1969
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    For the members of n-higher primary amines from C12 to C20 the crystal structure was studied by X-ray powder method. From the values of long spacings and the splitting of (110) reflections it was concluded that the structure is probably similar to that of fatty acids and that the hydrocarbon chains are tilted with respect to the plane formed by end groups. This structure seems to be stable over the temperature range between room temperature and melting points. The dependence of melting points on chain length was discussed.
  • Tadahiro Yamamoto, Masaru Hasegawa, Takayuki Otsu
    1969 Volume 42 Issue 5 Pages 1364-1367
    Published: 1969
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    In order to study the effect of substituents on the chain-transfer reactivities of nuclear-substituted benzaldehydes toward polymethyl methacrylate (poly-MMA) and polystyryl (poly-St) radicals, the chain transfer constants (C) of six kinds of benzaldehydes in radical polymerizations of these monomers were determined at 60°C. The C values of all the substituted benzaldehydes toward the poly-MMA radical were larger than that of unsubstituted benzaldehyde, regardless of the electron-repelling or electron-attracting nature of the substituents, while those toward the poly-St radical increased with an increase in the electron-attracting nature of the substituents. The relative reactivities toward the poly-MMA radical could not be correlated with the ordinary Hammett equation, but they could be with this modified equation: log(kk0)=ρσ+γER, with ρ=+0.2 and γ=0.7. On the other hand, the relative reactivities toward the poly-St radical also fit a modified Hammett equation with ρ=+1.4 and γ=0.65.
  • Hiroshi Kotake, Tomoo Saito, Kazuo Okubo
    1969 Volume 42 Issue 5 Pages 1367-1373
    Published: 1969
    Released: March 27, 2006
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    A diastereoisomeric mixture of racemic β-methylleucine was synthesized by the condensation of 2-benzyl-4(5H)-imidazolone with the methyl isopropyl ketone, followed by catalytic hydrogenation and hydrolysis. The separation of the mixture into threo-β-methyl-DL-leucine and erythro-β-methyl-DL-leucine was mainly achieved by fractional crystallization from water. The resolution of each diastereoisomer was also accomplished through salt-formation with (−)- and (+)-ephedrine alternately before or after the methylation of the amino group. The specific rotation and the NMR and IR spectra of one isomer, threo-N,β-dimethyl-L-leucine, corresponded closely with those reported for dimethylleucine isolated from nature.
  • Teruzo Asahara, M. C. Chou
    1969 Volume 42 Issue 5 Pages 1373-1377
    Published: 1969
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The radical telomerization of vinyl chloride with carbon tetrabromide was investigated. The telomers with n=1 and 2 in Br(CHClCH2)nCBr3 were isolated and identified. The molecular weight distribution of the telomers was determined by thin-layer chromatography (TLC), and it was found that the distribution varied a little with the variation of reaction conditions. From the results of the TLC, the chain transfer constants (Cn) of polylvinyl chloride radical to carbon tetrabromide were calculated, and a monotonous increase in Cn with the increasing n was found. The effects of initial ratio of vinyl chloride to carbon tetrabromide, reaction time and temperature on the conversion of vinyl chloride and the average molecular weight of the telomer were investigated. Bromoform was also used as a telogen instead of carbon tetrabromide, and the results were compared in both systems.
  • Noboru Sugiyama, Masaaki Iwata, Michikazu Yoshioka, Kazutoshi Yamada, ...
    1969 Volume 42 Issue 5 Pages 1377-1379
    Published: 1969
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    It was found that anthracene (I) was converted to 9,10-anthraquinone (III) and bianthrone (IV) by irradiation via anthracene peroxide (II). The reaction proceeded most effectively in carbon disulfide. Also IV was found to be oxidized to III by oxygen in singlet state.
  • Rokuro Sudo, Akira Kaneda, Nobuo Furuoya
    1969 Volume 42 Issue 5 Pages 1380-1382
    Published: 1969
    Released: March 27, 2006
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    The acyl derivative of oxime, derived from a strong acid, is generally unstable. However, acyl oximes of the ethyl α-oximinoacetate derivative were prepared and were found to be more stable than ordinary acyl oxime. Acetyl, carbethoxy, benzoyl, and even tosyl ester were prepared, and their reactions with the mercaptide anion were investigated.
  • Akira Misono, Yasuzo Uchida, Ken-ichi Furuhata, Shohei Yoshida
    1969 Volume 42 Issue 5 Pages 1383-1386
    Published: 1969
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Oligomerization of isoprene by the catalyst system consisting of hafnium(IV) n-butoxide and diethylaluminum chloride was studied. Isoprene was oligomerized to a mixture of dimers, trimers and higher oligomers. The compound, 2,6-dimethyl-1-trans-3,6-octatriene, was the main dimer of isoprene in this reaction. The maximum yield of this dimer in the reaction at 130°C for 2 hr was accomplished when the molar ratio of diethylaluminum chloride to hafnium(IV) n-butoxide was 4.7. The addition of tetrahydrofuran or triphenylphosphine kept the selectivity for the dimer nearly constant. These results were compared with those obtained by the catalyst system consisting of titanium (IV) n-butoxide or zirconium(IV) n-butoxide and diethylaluminum chloride.
  • Yoshimasa Kyogoku, Byung Sul Yu
    1969 Volume 42 Issue 5 Pages 1387-1393
    Published: 1969
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Riboflavin-2′,3′,4′,5′-tetraacetate and tetrabutyrate have been found to associate with 9-ethyladenine. They form stronger complexes with each other than with themselves and with other nucleic acid purine and pyrimidine derivatives. The association constants of the formation of the complexes were determined from the infrared spectra to be 130 and 95M−1 respectively. The complex is a 1 : 1 cyclic hydrogen bonded dimer through the imino and the 2-C carbonyl groups of the isoalloxazine ring and the amino group of the adenine residue. 9-Ethyladenine is an effective quencher of the fluorescence of riboflavin tetraacetate. The quenching appears mainly due to the coplanar interaction through hydrogen bonds and partly due to the collision interaction with the purine rings. Some barbiturates were found to prevent the formation of the complex of the adenine and riboflavin derivatives by the formation of more stable complexes with ethyladenine.
  • Shuji Inamasu, Michio Horiike, Yuzo Inouye
    1969 Volume 42 Issue 5 Pages 1393-1398
    Published: 1969
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Further evidence for the unambiguous solvent polarity dependence of the stereochemistry in the base-catalyzed Michael type condensation was provided by the systems involving (−)-menthyl chloroacetate and methyl acrylate, and (−)-menthyl chloroacetate and (−)-menthyl acrylate with a modification of the work-up. The electrostatic control of the stereoselectivity was interpreted by the same theorem developed in the previous study and some novel features found for the present systems were discussed.
  • Kenji Fukui, Takashi Matsumoto, Sachihiko Tanaka
    1969 Volume 42 Issue 5 Pages 1398-1403
    Published: 1969
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The acid-catalyzed isomerization of 4-benzyloxy-2′-hydroxy-3,4′,5′,6′-tetramethoxychalcone gave 4′-benzyloxy-3′,5,6,7-tetramethoxyflavanone, which was then converted by oxidation to 4′-benzyloxy-3-hydroxy-3′,5,6,7-tetramethoxyflavone. This, after debenzylation to 3,4′-dihydroxy-3′,5,6,7-tetramethoxyflavone, was partially demethylated with aluminum chloride or aniline hydrochloride to give 3,4′,5-trihydroxy-3′,6,7-trimethoxyflavone (I) (mp 213–214°C), the structure proposed previously for the chrysosplenetin (mp 177–178°C) isolated from Chrysosplenium japonicum Makino. However, the synthetic flavone was found to be different from natural chrysosplenetin by a mixed melting point determination and by a comparison of the spectra. Finally, the structures of chrysosplenetin and chrysosplenin were established by the spectroscopic studies to be 4′,5-dihydroxy-3,3′,6,7-tetramethoxyflavone (XIII) and its 4′-glucoside (XIV) respectively. The revised structure for chrysosplenetin has been fully confirmed by direct comparison with an authentic sample.
  • Shûichi Hayashi, Shinji Kurokawa, Tamon Matsuura
    1969 Volume 42 Issue 5 Pages 1404-1407
    Published: 1969
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Vetivazulene was heated with sulfur to give a new sulfur-containing azulene, 3,5,9-trimethylazuleno[1,2-b]thiophene. On Vilsmeier formylation, the compound normally resulted in the formation of 4-formyl derivative, while the acetylation according to the Vilsmeier procedure proceeded abnormally to produce 4-dimethylamino-3,5,9-trimethylazuleno[1,2-b]thiophene.
  • Kenji Fukui, Mitsuru Nakayama
    1969 Volume 42 Issue 5 Pages 1408-1411
    Published: 1969
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The reduction of medicagol methyl ether with lithium aluminum hydride in tetrahydrofuran yielded a diol. The dehydration of the diol in boiling diethylene glycol gave an ether (anhydropisatin, O-methyl anhydrosophorol). Then, the above ether was hydrogenated with 10% Pd-C to (±)-pterocarpin.
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