Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 43 , Issue 12
Showing 1-50 articles out of 84 articles from the selected issue
  • Hiroshi Yoneyama, Shi\v{n}iichi Hamamatsu, Hideo Tamura
    1970 Volume 43 Issue 12 Pages 3639-3643
    Published: 1970
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The redox reactions of Fe(CN)64−/Fe(CN)63−, Fe2+/Fe3+, and Ce3+/Ce4+ systems on α-Fe2O3 electrodes containing different amounts of titanium were studied. The anodic current showed a tendency to be saturated in the Fe(CN)64−/Fe(CN)63− and Fe2+/Fe3+ systems. The forward direction of the current flow in these systems was the reverse of the case with the lithiated NiO electrode. On the other hand, the cathodic current flow was negligible and the redox potential was not observed for the Ce3+/Ce4+ system. It was concluded that the reaction proceeds through electron transfer and that IV curves are determined by the influence of the potential barrier formed on the electrode surface over which an electron transfers from the electrode into the electrolyte or in the reverse direction.
  • S. P. Jain, S. N. Srivastava
    1970 Volume 43 Issue 12 Pages 3644-3650
    Published: 1970
    Released: March 27, 2006
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    A partially flocculated Fe(OH)3 sol has been used as an emulsifying agent to stabilize toluene/water system. The electrophoretic mobilities of the emulsion thus obtained in the presence of different anionic detergents have been measured microelectrophoretically and from these values the zeta potentials have been calculated. At the charge reversal concentrations the adsorption and free energy constants were calculated. From the surface potential values the repulsion and attraction energies were evaluated which clearly showed that the flocculation occurrs in the secondary minima. The operating van der Waals constant A has been estimated by correlating the results of degree of aggregation obtained haemocytometrically with the theoretical values. It was found to be 1.05×10−12 erg. The values of interfacial tension have been reduced by the addition of these detergents which are directly connected with the chain length of the detergent and adsorption characteristics.
  • D. S. Manikyam, E. V. Sundaram
    1970 Volume 43 Issue 12 Pages 3651-3652
    Published: 1970
    Released: March 27, 2006
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    Thermal decarboxylation of o-, m- and p-nitro benzoic acids was studied in glycerol in the temperature range 210–250°C m- and p-Nitrobenzoic acids exhibited first order rate constants and in support of the proposed SE1 mechanism, the isomers were also studied in aniline at 110–140°C. Pseudo-first order rate constants of the ortho isomer in glycerol suggested a change in mechanism from SE1 to SE2. The rate constants were influenced by boric acid or aniline added to glycerol as the result of a change in pH and confirmed thus the proposed SE1 or SE2 mechanisms. Activation energies, enthalpies and entropies of activation were obtained for the three isomers.
  • Akira Amano, Masao Uchiyama, Yoshiki Sato, Hiroo Tominaga, Hiromichi A ...
    1970 Volume 43 Issue 12 Pages 3653-3657
    Published: 1970
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Rates of demethylation of six different polymethylbenzenes have been measured, at 702°C and residence times ranging from 0.5 to 6.0 sec in the presence of five-fold in excess hydrogen, by using toluene as an internal reference. The rates per one equivalent methyl group were: 1.08 for p-xylene, 1.73 for o-xylene, 1.26 for 4-position of 1,2,4-trimethylbenzene, 1.87 for 2-position of 1,2,4-trimethylbenzene, 1.85 for 1-position of 1,2,4-trimethylbenzene, 1.20 for 1,3,5-trimethylbenzene, 2.22 for 1-positionof 1,2,3-trimethylbenzene, 3.25 for 2-position of 1,2,3-trimethylbenzene, 1.5 for 5-position of 1,2,3,5-tetramethylbenzene, 2.1 for 1-position of 1,2,3,5-tetramethylbenzene, and 2.8 for 2-position of 1,2,3,5-tetramethylabenzene. all the figures being expressed against the standard value of 1.00 for toluene. The observed accelerating effect of neighboring methyl groups on the demethylation rates of crowded reactant molecules has been correlated with modified superdelocalizability in z direction for radical aromatic substitution. The latter values calculated by the extended Hückel molecular orbital method were: 0.4070, 0.4116, 0.4908, 0.4169, 0.4124, 0.4116, 0.4131, 0.4133, 0.4148, 0.4204, 0.4120, and 0.4029 (toluene) in the order given above. The general parallelism between the observed and the theoretical values may be taken as a support not only of the extention of the concept of superdelocalizability to radical aromatic substitution, but also of our mechanistic interpretation on the key reaction of hydrogenolyses.
  • Hiroo Tominaga, Hiromichi Arai, Taiseki Kunugi, Akira Amano, Masao Uch ...
    1970 Volume 43 Issue 12 Pages 3658-3662
    Published: 1970
    Released: March 27, 2006
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    In hydrogenolysis of toluene to produce benzene and methane, atomic cracking process H+C6H5CH3→C6H6CH3 (a) or H+C6H5CH3→C6H5+CH4 (b) has been presumed as rate controlling in chain propagation step of the radical chain mechanism. These two alternative processes are compared on the energetics calculated by the extended Hückel M.O. method. The reaction (a), an addition of the attacking hydrogen atom to phenyl carbon atom adjacent to methyl group followed by an elimination of methyl radical in a concerted manner, is found to be the most likely pathway.
  • Yoshiyuki Kumata, Junji Furukawa, Takayuki Fueno
    1970 Volume 43 Issue 12 Pages 3663-3666
    Published: 1970
    Released: March 27, 2006
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    The change in the rotatory direction of optically active poly(propylene oxide) in different solvents has been discussed from the viewpoint of dielectric theory of solution. It has been pointed out that, in general, the shapes of the optical rotatory dispersion curves of polymers cannot directly be related to their conformation.
  • Masao Nakamura, Tsunetaka Sasaki
    1970 Volume 43 Issue 12 Pages 3667-3671
    Published: 1970
    Released: March 27, 2006
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    The relationship between surface activity and molecular structure has been studied for the nonionic polymeric surfactants which have 2,3,4 or 6 branches of polypropylene glycol-polyethylene glycol (PPG-PEG) chain in their molecules. A linear relation, 1⁄Δγ=A+B·xy has been found to hold for each series, where Δγ is the surface tension depression of surfactant solution of a given concentration from that of water, xy is the molecular structure index, in which x is the weight percent of PEG group in a molecule and y is the molar weight of PPG part, and A and B are constatns. Constant A, being equal to 0.025 cm/dyn, is independent of the concentration and the number of PPG-PEG branches and corresponds to the reciprocal of surface tension lowering of an aqueous solution of infinitely large PPG polymer. Constant B decreases linearly with the logarithm of molar concentration, and increases with the number of branches. It also depends on the hydrophilic nature of the central group of molecule.
  • Masaru Ichikawa, Mitsuyuki Soma, Takaharu Onishi, Kenzi Tamaru
    1970 Volume 43 Issue 12 Pages 3672-3679
    Published: 1970
    Released: March 27, 2006
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    The mechanism of the reaction between molecular hydrogen and the electron donor-acceptor complexes (ANa+ and A=2Na+) of various aromatic hydrocarbons (A) with sodium were studied kinetically and spectroscopically. The relative activity of each electron donor-acceptor (EDA) complex for the hydrogen uptake was associated with its electronic properties, especially with the reduction potential of its anion. It was found that the hydrogen molecule reacts more readily with stronger electron-donating EDA complexes, whose anions have higher reduction potentials. It was also suggested that, on the hydrogen adsorption over the ANa+ and A=2Na+ films (or in their solutions), the corresponding monohydroanion complexes (AHNa+) and NaH were produced as follows :
    &2A^-Na^++H_2=AH^-Na^+NaH+A
    &A^=2Na^++H_2=AH^-Na^++NaH
    The behavior of AHNa+ was closely correlated with the localization energies of electrons in the anions of the aromatic hydrocarbons.
  • Makoto Misono, Yasukazu Saito
    1970 Volume 43 Issue 12 Pages 3680-3684
    Published: 1970
    Released: March 27, 2006
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    Utilizing the dual parameter equation we derived previously, we have evaluated quantitatively softness or class (b) character of metal ions on the basis of the original criteria of soft-hard classification, viz., the stability of metal-ion complexes. Various softness parameters proposed so forth have been proved insufficient to describe softness quantitatively, although they are useful for a rough classification of metal ions into soft and hard acids. Discussion is also given concerning origin of softness, especially from the viewpoint of its closs correlation with the solvation effect.
  • Yôichi Iida
    1970 Volume 43 Issue 12 Pages 3685-3688
    Published: 1970
    Released: March 27, 2006
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    The phase transitions of the anion radical salts containing mixed cations represented by [(C6H5)3PCH3]1−x+[(C6H5)3AsCH3]x+(TCNQ)2\ ewdot, (0≤x≤1) were investigated. The transition temperature, Tc, and the magnitude of the heat, ΔH, of the transition were determined as a function of the composition parameter, x, by means of a differential scanning calorimeter. It was found that Tc increases, and ΔH decreases, monotonously with an increase in the value of x, and that the phase transition disappears with x=1.00. The mechanism of the phase transitions was discussed on the basis of the theory of triplet exciton-exciton interaction proposed by Chesnut. The theoretical values of the entropy changes of the transitions were found to be much less than those observed. In view of these results, it was concluded that the anomalies in the magnetic susceptibilities of these salts were induced by the change in the crystal structure.
  • Masamoto Iwaizumi, Taro Isobe
    1970 Volume 43 Issue 12 Pages 3689-3694
    Published: 1970
    Released: March 27, 2006
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    The 5,12-dihydrotetracene radical anion and its ion pairs with alkali-metal cations have been Investigated by electron spin resonance (ESR). It has been found that the frequency of the inversion of the radical molecule is >>108 Hz and that the unpaired electron is distributed between the benzene and naphthalene rings. Such a distribution of the unpaired electron between the two conjugated systems is assumed to occur via a hyperconjugation mechanism. On the other hand, it was observed that the proton hyperfme splittings of the radical anion are appreciably affected by the association of an alkali-metal cation. In the case of the 5,12-dihydrotetracene-potassium ionpair in THF, the hyperfine components of the methylene protons show an alternating line-width effect. On the basis of the observed effects of the alkali metal cations, a model of the ion-pair structure is proposed, and the alternating line-width effect is explained in terms of an intramolecular migration of the potassium ion from one side of the molecular plane to the other. The activation energy of this motion of the potassium ion has been estimated to be 3.1±0.2 kcal.
  • Chiaki Hirose
    1970 Volume 43 Issue 12 Pages 3695-3698
    Published: 1970
    Released: March 27, 2006
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    The microwave spectra of vinylacetylene, CH2CHCCH, and monodeutero-vinylacetylene, CH2CHCCD, have been observed in the ground state and several vibrational excited states. The vibration-rotation constants α1(a), α1(b), α1(c), α2(a), α1(b), and α1(c), have been obtained as 1 370, −18.32, −7.73, −907, −2.78, and −8.97 MHz for CH2CHCCH, and 2 010, −16.66, −7.05, −1640, −2.18 and −7.84 MHz for CH2CHCCD, respectively, the error limits being ±50 MHz for α(a)’s and ±0.03 MHz for α(b)’s and α(a)’s. Electric dipole moments obtained are 0.223±0.020 and 0.206±0.008 Debye for CH2CHCCH and CH2CHCCD, respectively, which are quite different from the values reported previously.
  • Hisashi Ueda, Naoyuki Todo
    1970 Volume 43 Issue 12 Pages 3698-3705
    Published: 1970
    Released: March 27, 2006
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    This work was planned in order to determine the reaction mechanism of the catalytic, direct desulfurization of organic sulfur compounds on the surface of Al2O3-MoO3-CoO particles. The experimental method consists of quantitative ESR measurements, by means of which the paramagnetic species on the surface of Al2O3, Al203-MoO3, and Al2O3-MoO3-CoO in the presence and in the absence of H2 and thio-β-naphthol were studied. As it is expected that, in an ideal and fast-reacting catalytic reaction system, no reaction intermediate can be found because it will be immediately converted to the final product, several artificial reaction systems were investigated in which either one of the reactants, catalyst components, or reaction conditions (e. g., temperature) was deficient. In such deficient systems, the reaction cycle is cut off and some intermediates are expected to accumulate. The paramagnetic species observed were Co3+, Mo5+, thio-β-naphthol+-O*2− or RS+H–O*2−, and some species formed on the surface of Al2O3, in the temperature region of 20°C–200°C. Mo6+ is concluded to be the electron trap to facilitate the formation of RS+H–O*2−, Co3+ is concluded to oxidize the Mo5+ thus formed to Mo6+, and Co2+ is concluded to reduce the R-S+H2–O*2− species. The latter then decomposes to H2S and R·.
  • Makoto Kawabe, Osamu Ohashi, Ichiro Yamaguchi
    1970 Volume 43 Issue 12 Pages 3705-3710
    Published: 1970
    Released: March 27, 2006
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    The phosphorus nuclear magnetic resonance spectra of several condensed phosphates (polyphosphates) were measured in aqueous solutions. The NMR spectra generally consist of three peaks which correspond to the phosphorus atoms at the end and middle of the molecular chain and in orthophosphoric acid which is the final product of the hydrolysis. The chemical shift and, for some phosphates, spin-spin coupling constants were obtained. Both depend on pH of the solution. The chemical shifts for the end and middle phosphorus atoms depend also on the chain length of the molecule. The hydrolysis process of the phosphates can be traced by the observation of the time dependence of spectral line intensities. From this observation the rate constant of the hydrolysis is obtained for several phosphates. The values are comparable with those obtained by other methods.
  • Takefumi Oka, Shin Sato
    1970 Volume 43 Issue 12 Pages 3711-3715
    Published: 1970
    Released: March 27, 2006
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    The 60Co γ-radiolysis of liquid nitrogen containing ethylene has been reinvestigated in order to elucidate the mechanism of the formation of nitrogenous products. When the conversion of ethylene was 10%, the G-values of hydrogen cyanide and acetonitrile were 0.21±0.03 and 0.05±0.01 respectively. The isotopic distributions in acetonitrile, n-butane, and acetylene were examined by using an equimolar mixture of C2H4 and C2D4 as the solute. From the analysis of these distributions, it has been concluded that acetonitrile is produced mainly from the reaction between nitrogen atoms and ethyl radicals.
  • Tsutomu Kagiya, Y\={u}z\={o} Sumida, Toshihiro Tachi
    1970 Volume 43 Issue 12 Pages 3716-3722
    Published: 1970
    Released: March 27, 2006
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    The relationship between the proton-donating and proton-accepting powers and the structures of various proton donors and acceptors was studied in the liquid phase by means of an infrared spectrophotometer. The proton-donating powers of the donors were evaluated by means of the ratios of the O–H shifts of the donors (RO–H) to those of methanol in various proton acceptor solutions. The proton-accepting powers of the acceptors were evaluated by means of the division of the O–H shifts by the proton-donating powers of the donors used. The proton-donating powers increased with the decrease in the pKa or the ionic RO–H bond dissociation energies and with the increase in the electron affinities of RO radicals, i. e., t-butanol<methanol<<trimethylsilanol<phenol<p-nitrophenol. In a homologous series, the proton-accepting powers increased with the decrease in the ionization potentials. In the case of the aromatic ethers with two proton accepting sites, two characteristic O–H vibrational bands were observed. The difference in the protonaccepting powers of the vinyl and ethyl compounds with the same substituent was observed, and the π-electron-mobility index, which was considered to be a measure of the energy level of the π-electrons of the vinyl group, was defined and discussed.
  • Otohiko Nomoto, Harumi Endo
    1970 Volume 43 Issue 12 Pages 3722-3728
    Published: 1970
    Released: March 27, 2006
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    The sound velocity and density of polyoxyethylene(6)lauryether and its aqueous solutions are measured, and the adiabatic compressibility is computed from these results. The virtual sound velocity was calculated in ideal mixtures by using Kudriavtsev’s formula, and above 33°C for ideal suspensions by the use of the equation of Urick and Ament for dispersed systems. Some deviations in the experimental velocity from the calculated value are ascribed to the interaction energy of mixing. This energy, or the heat of the hydration of a nonionic surfactant, is obtained as a function of the temperature. The diagrams of the density, sound velocity, and adiabatic compressibility vs. the temperature at various concentrations always exhibit a common crossing point, nearly at the cloud point. It may thus be concluded that the measurements of the sound velocity and density give a new method for determining the cloud point.
  • Kyoji Shinsaka, Shoji Shida
    1970 Volume 43 Issue 12 Pages 3728-3740
    Published: 1970
    Released: March 27, 2006
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    The effects of various additives, SF6, NH3, C2H5OH, N2O, NO, SO2, and C2H4, on the product yields in the γ-radiolysis of liquid n-hexane at room temperature have been investigated. The following conclusions have been drawn: (i) The added SO2 acts mainly as a radical scavenger. (ii) The added NO shows not only the effect of radical scavenging, but also other effects. Therefore, it is inadequate to use NO as a simple radical scavenger, (iii) The C7-C12 products are formed from a combination reaction of alkyl radicals, but not from an ion-molecule reaction, (iv) The formation of C6H13+ ions by the direct action of radiation is suggested, (v) The G-value of ionization is evaluated to be 4.0. A brief discussion concerning the formation of N2 in the presence of N2O is also given.
  • Akihiko Yamagishi, Mitsuyuki Soma
    1970 Volume 43 Issue 12 Pages 3741-3745
    Published: 1970
    Released: March 27, 2006
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    The temperature dependence of dark- and photo-currents was studied for the hole injection into anthracene crystals between 0 and 30°C. It was observed that the photocurrent or, as has been previously established, the electron-transfer rate from an excited anthracene crystal to an acceptor had a small temperature dependence, while the dark current or the electron-transfer rate from the crystal in its ground state to an acceptor had a definite value of activation energy. The observed small activation entropy for the dark reaction was interpreted in terms of Marcus’ theory, and the small polarizability of the organic crystal was, accordingly, suggested to increase the probability of the electron transfer.
  • Tetsuo Morimoto, Mahiko Nagao
    1970 Volume 43 Issue 12 Pages 3746-3750
    Published: 1970
    Released: March 27, 2006
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    In the system ZnO-H2O, in which a jump appears in the adsorption isotherm, the relation between the amounts of chemisorbed and physisorbed water has been investigated, on the basis of the measurements of the water adsorption isotherms and the water content. The first adsorption isotherm of water was measured at 18°C on a sample degassed at 450°C. After degassing the sample again at 30°C, the second adsorption isotherm was obtained at the same temperature as before. The water content (Vh) on the surface of the sample was determined by the successive ignition-loss method. In the present system, the amount of water physisorbed in the first layer is composed of two parts: one (Vp1) is the amount adsorbed at lower vapor pressures, up to the beginning of the jump in the isotherm, and the other (Vp2), the amount adsorbed during the jump. The amount of water chemisorbed (Vc) during the adsorption process could be estimated as the difference between the monolayer capacities of the first and second isotherms, the total amount of chemisorbed water being the sum of Vh and Vc. The ratio of the total amount of physisorbed water (Vp1+Vp2=Vp), expressed in the number of water molecules per unit of area, to that of chemisorbed water (Vc+Vh), expressed in the number of hydroxyl groups per unit of area, was found to be about 1 : 1 in the first physisorption layer for all the samples tested, irrespective of their origin, while the ratio of Vp1 to Vp2 varied extensively with the origin of the samples.
  • Ariyuki Aihara, Chikazu Kitazawa, Akira Nohara
    1970 Volume 43 Issue 12 Pages 3750-3754
    Published: 1970
    Released: March 27, 2006
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    Dielectric measurements have been performed with pentachloronitrobenzene in polycrystalline state using a trans-former bridge, between 30 Hz and 1 MHz and in the temperature range 20–99°C. The substance shows distinct dielectric absorption in the frequency and temperature ranges, presumably due to molecular rotation in the solid state similar to that of pentachlorotoluene and 1,2,4-trimethyl-3,5,6-trichlorobenzene as has been found by Turney. The frequency factor and the energy of the barrier for the rotation are logA=15.2 (A in sec−1) and ΔH=16.1 kcal/mol. A possible mechanism for the rotational transition of the molecule in the crystalline lattice has been discussed. The dipole moment of this substance in benzene solution has been measured, the result being μ=2.33 Debye.
  • Hiroko Yamabe, Hiroshi Kato, Teijiro Yonezawa
    1970 Volume 43 Issue 12 Pages 3754-3761
    Published: 1970
    Released: March 27, 2006
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    The electronic structure and the electronic transition of thiothiophthene(I) and 2,5-dimethyl-dithiofurophthene(II) are calculated by the semi-empirical ASMO SCF method. The EAB value, used instead of the bond order of the S···S bond of Compound I, and those of the S···S bond and the S···O interaction of Compound II are found to be −6.125 eV, −12.957 eV, and −0.740 eV respectively. These EAB values are compared with that of the previously-obtained transannular interaction and the hydrogen bond of water dimers calculated by the same method. The properties of the electronic transition of these compounds are discussed. No separability of the π–π*(B2)-type and σ-σ*(B2)-type transitions of the Compound I is indicated. The orbital energy of the highest occupied MO of the Compound I is remarkably high, which corresponds well with the very small Ip value.
  • Terunobu Wakayama, Tetsuo Miyazaki, Kenji Fueki, Zen-ichiro Kuri
    1970 Volume 43 Issue 12 Pages 3761-3765
    Published: 1970
    Released: March 27, 2006
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    The present work was undertaken in order to examine intermediates from benzene and toluene in γ-irradiated glassy methylcyclohexane (MCH) and polycrystalline isobutane matrices at 77°K. The γ-irradiation of MCH containing low concentrations of benzene gave an ESR spectrum with a good hyperflne resolution, which can be ascribed to the benzene anion, while at higher concentrations of benzene it gave an ESR spectrum with a poor resolution, which is attributable to the benzene monomer and dimer anions. On the contrary, the γ-irradiation of polycrystalline isobutane containing benzene did not yield an ESR spectrum which can be attributed to the benzene anion. However, the γ-irradiation of a mixed glass of isobutane and 4 mol% MCH containing benzene gave an ESR spectrum which is attributable to the benzene anion. The yield of trapped electrons in this system was three times as large as that in pure γ-irradiated MCH. Such a difference in the results between glassy MCH and polycrystalline isobutane matrices gives evidence of a phase effect on the radiolysis of solid hydrocarbon.
  • Mitsufusa Hori, Hiroyasu Itoi, Hiroshi Tsubomura
    1970 Volume 43 Issue 12 Pages 3765-3773
    Published: 1970
    Released: March 27, 2006
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    Flash photolysis of aniline derivatives in various solutions has been studied in oxygenated and deoxygenated conditions. Absorption spectra of the triplet states appeared in deoxygenated liquid paraffin solutions, but no transient absorption was observed in the oxygenated liquid paraffin solutions. Transient spectra, due to the cations of the anilines, were observed in deoxygenated ethanol solutions, but none in oxygenated ethanol. In highly polar solvents—acetonitrile, water, and formamide—either deoxygenated or oxygenated, the cation was observed. In the case of oxygenated solutions, the initial yield of the cation was found to be proportional to the intensity of the flash light, indicating that the ionization is a one-photon process. These results, together with the previous findings that the photo-ionization of organic molecules in solutions are caused by the two-step, biphotonic excitation processes strongly suggest that the charge transfer states are formed between the aromatics and the oxygen molecule, either by direct excitation or via the interaction of excited anilines and the ground state of oxygen, and the charge transfer states then lead to the solvated cations and anions in highly polar solvents. The decay of the ions have been found to follow the second order kinetics.
  • Jiro Higuchi
    1970 Volume 43 Issue 12 Pages 3773-3779
    Published: 1970
    Released: March 27, 2006
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    The effect of the methylene bond angles on the electron spin-spin interaction has been semiempirically investigated for the quintet ground states of the m-phenylene-dimethylene radicals, especially m-phenylene-bismethylene and m-phenylene-bisphenylmethylene. The D and E values calculated are compared with those observed, and the most probable structure, with a methylene bond angle near 140°, is estimated, as in the phenylmethylene radical.
  • Kay Kohn, Ichiro Nakagawa
    1970 Volume 43 Issue 12 Pages 3780-3789
    Published: 1970
    Released: March 27, 2006
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    The infrared absorption spectra of RbNiF3 and CsNiF3, both with a perovskite-like structure, have been measured in the region 500–50 cm−1 at room temperature and at liquid nitrogen temperature. The observed bands can be classified into three groups, corresponding to the three absorption bands in perovskite. These bands can reasonably be assigned on the basis of the crystal symmetry of the investigated compounds. A normal coordinate analysis of a crystal as a whole has been performed, where the interatomic force constants between the atom pairs within a distance of 3.5 Å are taken into account. It was shown that the normal coordinate treatment of the opticallyactive vibrations on the basis of a molecular dynamics model is useful for the interpretation of the lattice vibrations in these fluorides. The effects of the structural differences of the lattice vibrations are discussed.
  • Hiroyasu Ichikawa, Muraji Shibata
    1970 Volume 43 Issue 12 Pages 3789-3793
    Published: 1970
    Released: March 27, 2006
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    Two new nitro complexes of cobalt(III), K2[Co(NO2)2CO3acac]·H2O and K3[Co(NO2)4CO3]·H2O, have been prepared by the reaction of tricarbonatocobaltate(III) and the desired ligand. The 700–200 cm−1 region IR spectra for these complexes and the other related dinitro complexes have been measured, and the geometrical structures of these dinitro complexes have been determined as of the cis-form on the basis of the IR data. Furthermore, the absorption spectra of these nitro complexes have also been measured, and the stability of these complexes has been related to the spectral data.
  • M. A. Siddiqui, M. K. Bhatty, Muhammad Ashraf
    1970 Volume 43 Issue 12 Pages 3794-3795
    Published: 1970
    Released: March 27, 2006
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    Nitrogen in organic compounds, agricultural and animal products is converted into ammonium sulphate by Kjeldahl digestion. The ammonium sulphate is reacted quantitatively with hypobromite produced in situ by the addition of an excess of potassium bromate and bromide. The unutilized potassium bromate is determined iodometrically and the amount of ammonia nitrogen can be calculated from the consumed potassium bromate. Accurate results are also obtained when potassium bromate is replaced with potassium permanganate or dichromate for the determination of ammonia nitrogen in Kjeldahl digests. However, the present method is not applicable to the determination of ammonia nitrogen in undigested sample.
  • Norinobu Yonehara, Minoru Yoshida, Iwaji Iwasaki
    1970 Volume 43 Issue 12 Pages 3796-3800
    Published: 1970
    Released: March 27, 2006
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    A rapid and sensitive method for the determination of minute amounts of iodine in silicate rocks has been developed. A rock was fused with potassium hydroxide, and the cake was treated with water and sulfuric acid. The iodine in the solution was reduced to iodide by sodium sulfite, and was then oxidized to free iodine by sodium nitrite. The free iodine thus obtained was extracted with carbon tetrachloride and then back-extracted with a sodium hydroxide solution. The iodine in this aqueous layer was determined photometrically by a method based on the catalytic effect of iodine on the color-fading of ferric thiocyanate. By the proposed method, amounts of iodine as low as 0.007 μg in a 1-g sample of silicate rocks can be determined. Application to some igneous rock samples gave results with a relative standard deviation of less than 7.2%, except for very low concentrations.
  • Keiji Matsumoto, Shun’ichiro Ooi, Hisao Kuroya
    1970 Volume 43 Issue 12 Pages 3801-3804
    Published: 1970
    Released: March 27, 2006
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    The crystal structure of cis-(+)589-[CoCl2en2]Cl·H2O has been determined by the X-ray-diffraction method. The crystal is monoclinic with the cell constants: a=12.07, b=11.52, c=8.33 Å, and β=96.9°. The space group is P21 and Z=4. There are two crystallographically-independent complexes in the unit cell, but they have the same configuration and almost identical molecular dimensions. The absolute configuration of the complex cation is consistent with that proposed by McCaffery, Mason and Norman and should be denoted as Λ(δδ).
  • Masao Mukaida
    1970 Volume 43 Issue 12 Pages 3805-3813
    Published: 1970
    Released: March 27, 2006
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    The complexes formed by the reactions of nitrosylrutheniurn(III) in hydrochloric acid solutions with tin(II) chloride were investigated. The following reaction products, (Me4N)2[RuCl3(SnCl3)2-NO], [1]; (Me4N)4[RuCl6(SnCl3)2(NO)2]·H2O, [2]; (Me4N)4[RuCl(SnCl3)5], [3] and K3[Ru2-Cl8(H2O)2N], [4] were isolated as crystals and were characterized. On the basis of chemical and thermal analyses, and on the basis of observations of the magnetic properties, the conductivities, and the infrared spectra, it was concluded that complexes [1], [2], and [3] contain terminal or bridging nitrosyl groups and/or a coordinating SnCl3 group, and that complex [4] contains a bridging nitrido group. The presence of the binuclear complex, “K3[Ru2Cl9(NO)2],” which has both the terminal and singly-bridged nitrosyl groups was also suggested. The relations among those complexes were discussed.
  • Yuzo Nishida, Sigeo Kida
    1970 Volume 43 Issue 12 Pages 3814-3819
    Published: 1970
    Released: March 27, 2006
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    Using optically active 1,2-propylenediamine we have synthesized several ligands to form square planar Cu(II) and Ni(II) complexes with optical activity. The CD (circular dichroism) and AB (absorption) spectra of these compounds were measured. The broad absorption bands were resolved in the CD spectra into each component due to a d-d transition, to which a specific d-d transition was assigned. It was found that in these compounds the change in the central atom from Cu(II) to Ni(II) dose not alter the main feature of CD and AB spectra. This seems to be the general rule for the planar Cu(II) and Ni(II) complexes.
  • Kiyoshi Kawasaki, Junko Yoshii, Muraji Shibata
    1970 Volume 43 Issue 12 Pages 3819-3823
    Published: 1970
    Released: March 27, 2006
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    The reaction of the carbonatobis(glycinato)cobaltate(III) with L-aspartate in the presence of active charcoal led to the stereoselective formation of tris(glycinato-L-aspartato) complexes. By means of ion-exchange chromatography and fractional precipitation, four optically-active complexes, mer-Λ- and fac-Δ-[Co(gly)3−n(L-asp)n]n (n=1,2), have been isolated, and they have been characterized by means of their absorption and circular dichroism spectra. Furthermore, the percent compositions of the geometrical isomers for the complexes (n=1,2,3) in the reaction mixture and also of Λ- (or Δ-) isomers for each geometrical isomer have been estimated using the spectral data. A marked stereoselectivity (>90%) has been found in the fac-Δ-isomers, while an appreciable selectivity (ca. 70%) has been found for the mer isomers. These stereoselectivities have been explained in terms of an enhanced stability through hydrogen bonding between the β-carboxylate group in the coodinated L-aspartate and the amino group in the adjacent ligand.
  • Hiromitsu Masada, Mitsuyuki Mizuno, Sohei Suga, Yoshihisa Watanabe, Yo ...
    1970 Volume 43 Issue 12 Pages 3824-3829
    Published: 1970
    Released: March 27, 2006
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    Potassium iron carbonylate, KHFe(CO)4, reacted with ethyl acrylate, crotonate, 3-butenoate, styrene, and α-olefins at 40–70°C under an atmosphere of carbon monoxide. Methylmalonate was selectively obtained from the acrylate by treatment of the reaction mixture with an alcoholic iodine and hydrogen chloride solutions. Dipotassium iron carbonylate, K2Fe(CO)4, reacted with β-bromopropionate to give mainly methylmalonate. Isomerization of β-ethoxycarbonylpropionyliron carbonylate to the α-isomer occurred readily in contrast to isomerization of acylcobalt carbonyl. Both crotonate and 3-butenoate gave ethylmalonate as a major product and methylsuccinate and glutarate as minor ones. The results suggest that α-ethoxycarbonylbutyliron carbonylate is more predominant than the corresponding β- and γ-isomers in equilibrium state. This is in striking contrast to the case of acylcobalt carbonyl. Styrene yielded two isomeric aldehydes, α- and β-phenylpropionaldehydes. Ethyl caproate and enanthate were obtained from 1-pentene and 1-hexene, respectively in poor yield.
  • I. P. Varshney, K. M. Shamsuddin
    1970 Volume 43 Issue 12 Pages 3830-3840
    Published: 1970
    Released: March 27, 2006
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    Acacic acid, a pentacyclic triterpenic acid, is present as a saponin in various members of the family Leguminosae, but the highest yield is obtained from the pods of Acacia concinna DC. On the basis of degradative studies, transformations, IR, UV, NMR, mass spectrography, and ORD, and CD studies its absolute stereochemistry and structure have been fixed as 3β, 16β, 21β-trihydroxy-18β-olean-12-en-28-oic acid and that in the acetate the rings E and D are in boat and quasi-boat forms, respectively, with D/E rings cis fused.
  • Kalyan K. Sengupta, A. K. Chatterjee, S. P. Moulik
    1970 Volume 43 Issue 12 Pages 3841-3845
    Published: 1970
    Released: March 27, 2006
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    The kinetics of chromic acid oxidation of glycollic and benzilic acids have been studied. Catalysis by H+ ions has been noticed in both cases of oxidation. The results show that the logarithm of the rate constants increases with increase in the proportion of acetic acid in the mixture. Ionic strength decreases the rate of oxidation. Pyridine catalyzes the oxidation of glycollic acid whereas the catalysis in the case of benzilic acid is negligible. The energy of activation and entropy of activation have been calculated. Both kinetics and spectrophotometric results indicate the formation of intermediate chromium (VI)-hydroxycarboxylate complex in each case. The complex finally decomposes to give reaction products. Glycollic acid initially produces glyoxylic acid which subsequently gives formic acid whereas benzilic acid is oxidized to benzophenone.
  • Yoshiaki Furuya, Kazuo Itoho, Sakiko Fukutaka
    1970 Volume 43 Issue 12 Pages 3846-3849
    Published: 1970
    Released: March 27, 2006
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    The rate of the hydrolysis of 1,3-diphenylurea (abbreviated as DPU) in dioxane in the presence of triethylenediamine (TED) was followed by ultraviolet spectrophotometry. The rate of the reaction satisfied the following equation:
    v=&{k_2-k_3h[H_2O]}[DPU][H_2O]+{k_4uh[H_2O]-k_3u}[DPU]^2[H_2O]
    &+{k_3c-k_4ch[H_2O]}[TED][DPU][H_2O]+{k_5cuh[H_2O]-k_4cu}
    &×[TED][DPU]^2[H_2O].
    A probable mechanism which involves a nucleophilic attack of the lone pair of the O-atom of water and of the N-atom of TED on the carbonyl C-atom of DPU, passing through an ion pair of quaternary ammonium salt, is discussed.
  • Shuichi Suzuki, Yutaka Hachimori, Ryuichi Matoba
    1970 Volume 43 Issue 12 Pages 3849-3852
    Published: 1970
    Released: March 27, 2006
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    The enzymic activity of Taka-amylase A on amylose, as measured by the blue-value method, increased to 180% of the original when one mole of mercaptosuccinyl group was introduced into one mole of the enzyme. Similar results were obtained for the activity measured by the Semogyi-Nelson method; the introduction of one or two mercaptosuccinyl groups raised the activity to 130–140% of that of the native enzyme. Even after the attachment of six mercaptosuccinyl groups per mole, the activity was 120% of the original. However, the enzymic activity was not elevated, but was lowered, by succinylation. When the sulfhydryl groups of the mercaptosuccinyl groups were blocked with p-chloromercurybenzoate or iodoacetamide, the enzyme was inhibited. These results suggest that the sulfhydryl groups of mercaptosuccinyl residues play an important role in increasing the enzymic activity.
  • Takayoshi Iio, Sho Takahashi, Shoyu Kobayashi
    1970 Volume 43 Issue 12 Pages 3853-3857
    Published: 1970
    Released: March 27, 2006
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    A copolymer consisting 95.8% of L-proline and 4.2% of O-benzyl-L-tyrosine was transformed in conformation from Form I to Form II as the propanol content changed from 100% to 74%. In Form I, the copolymer took a rod-like structure like that of poly-L-proline Form I, and the O-benzyl-L-tyrosyl residue moved independently of the molecular motion of the copolymer. On the other hand, the copolymer became flexible in Form II and the components associated with each other, forming an amorphous aggregation, when the propanol content decreased further, below the transition point. The hydrophobic interaction between the O-benzyl-L-tyrosyl side chain and the prolyl residue was the main factor which made the components of the copolymer associate with each other and form an amorphous aggregation. This was verified by a fluorescence study of the O-benzyl-L-tyrosyl residue.
  • Shinnichiro Suzuki, Ken-ichi Watanabe
    1970 Volume 43 Issue 12 Pages 3858-3861
    Published: 1970
    Released: March 27, 2006
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    The hydrolysis of three dipeptides, Gly-Gly, Gly-L-Leu, and Gly-L-Phe, with metal oxide catalysts was studied. In most cases, the hydrolysis occurred in the pH range 5–6 accompanied by the formation of metal complexes of amino acids and dipeptides. Copper oxide, nickel oxide, cobalt oxide (III), and alumina have more catalytic activity than copper powder, cuprous oxide, commercial nickel oxide (II), and silica gel. Alumina and silica gel gave no metal complex. It is assumed that the hydrolysis proceeds by means of the formation of an active metal complex of dipeptide or by means of activation on the surface of the catalyst. The order of reactivity of the dipeptides was: Gly-Gly>Gly-L-Leu, Gly-L-Phe.
  • Toshio Nakagawa, Tohru Sakakibara, Frieder W. Lichtenthaler
    1970 Volume 43 Issue 12 Pages 3861-3865
    Published: 1970
    Released: March 27, 2006
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    On treatment of lr,3c-diacetoxy-2t-nitrocyclohexane (3) or its 1,3-dimesyloxy analogue 4 with primary amines or ammonia, nitrodiamines (511) are obtained via an elimination-addition mechanism. Similar aminations of lr-methyl-1-nitrocyclohexane-2c,6c-diol (15) or its di-O-acetate 16 give C-methyl branched nitrodiamines (1214), which are also formed by reaction of glutaraldehyde with nitromethane and amines. Structures and conformations of the products obtained were deduced from IR and NMR data.
  • Toshio Nakagawa, Yoshikuni Sato, Tetsuyoshi Takamoto, Frieder W. Licht ...
    1970 Volume 43 Issue 12 Pages 3866-3869
    Published: 1970
    Released: March 27, 2006
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    A facile synthesis of methyl and phenyl glycoside derivatives of 2,3,4-triamino-2,3,4-trideoxy-β-D-glucopyranose is described, involving as the integral part the diamination with benzylamine or ammonia of 2,4,6-tri-O-acetyl-3-deoxy-3-nitro-hexosides of gluco- and galacto-configuration.
  • Hajime Suzuki
    1970 Volume 43 Issue 12 Pages 3870-3872
    Published: 1970
    Released: March 27, 2006
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    The ester-urethane interchange reaction has been studied by means of gas chromatography and NMR. The interchange reaction between low-molecular-weight ester and urethane was confirmed by the gas chromatography. Alternating copolyester-urethane was prepared by reacting bis-(hydroxyethyl)terephthalate with hexamethylene diisocyanate in anisole. When the polymer is melted at 190°C in the presence of sulfuric acid as a catalyst, the ester-urethane interchange reaction in alternating copolyester-urethane proceeds and causes a more random arrangement of the segments. This was proved by high-resolution nuclear magnetic resonance spectroscopy. An ethylene glycol residue adjacent to terephthalate on both sides, to diisocyanate on both sides, and to terephthalate and diiosyanate could be identified at 4.93, 4.48, and 4.71 ppm respectively in trifluoroacetic acid.
  • Ken Inouye, Kunio Watanabe, Keiko Namba, Hideo Otsuka
    1970 Volume 43 Issue 12 Pages 3873-3882
    Published: 1970
    Released: March 27, 2006
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    The synthesis and biological properties are described of an octadecapeptide amide, α-aminoisobutyryl-tyrosyl-seryl-methionyl-glutamyl-histidyl-phenylalanyl-arginyl-tryptophyl-glycyl-lysylprolyl-valyl-glycyl-lysyl-lysyl-arginyl-arginine amide, corresponding to the first eighteen amino acid residues of corticotropin (ACTH) except for the amino terminal residue. The amino-terminal decapeptide as intermediate is built up from a tripeptide (positions 1–3) and a heptapeptide (4–10), where a benzyloxycarbonyl and a benzyl ester groups are used for protection of the terminal α-amino group and the γ-carboxyl group of 5-glutamic acid, respectively. These protecting groups are removed in the final step with hydrogen fluoride. The new method is successfully applied to the corresponding 1-β-alanine octadecapeptide amide, which has been synthesized previously by a different procedure. Adrenal-stimulating properties of the 1-α-aminoisobutyric acid peptide are compared with those of the 1-β-alanine peptide to show that the former peptide is more active than the latter when assayed by the adrenal-ascorbic acid depletion and the in vivo steroidogenesis methods. The lipotropic activity of the new peptide is also shown to be more prolonged than that of the 1-β-alanine peptide.
  • Takeshi Nakai, Makoto Okawara
    1970 Volume 43 Issue 12 Pages 3882-3886
    Published: 1970
    Released: March 27, 2006
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    The reaction of 2-methylthio-1,3-dithiolanylium ion (III) with N,N-dimethyldithiocarbamate anion (SN) has been studied with a view toward demonstrating the ambident character of the cation III. It was found that (i) the reaction afforded S-β-(N,N-dimethyldithiocarbamyl)ethyl-S′-methyltrithiocarbonate (IV; normal) together with ethylene bis(N,N-dimethyldithiocarbamate) (V; abnormal); (ii) methylthioxanthate anion (SS) was formed in the reaction; (iii) the formation of the abnormal product (V) was more favorable and this could not be ascribed to the attack of SN on the normal product (IV). The ambident reactivity of cation III has been compared with that of closely related cations, tris(methylthio)carbonium ion and 2-methylamino-1,3-dithiolanylium ion (Ia). It was also found that the reaction of Ia with ethylthioxanthate anion (SS′) afforded the S′-ethyl analog of IV (normal) together with a small amount of abnormal V. The mechanism for the formation of the abnormal product (V) both from III and SN and from Ia and SS′ has been suggested.
  • Juji Yoshimura, Takao Iida, Masuo Funabashi
    1970 Volume 43 Issue 12 Pages 3887-3891
    Published: 1970
    Released: March 27, 2006
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    Condensation of acyclic or cyclic β-nitroalcohols with aldehydes was examined. In the case of non-protected 1-deoxy-1-C-nitro-D-glycitols and benzaldehyde, products caused by aldehyde-exchange reaction were obtained. However, the reaction of 2-methoxy-1-nitropentane or non-protected 2-nitrocyclohexanol and reactive aldehydes (formaldehyde, acetaldehyde and n-butyl glyoxylate) in the presence of sodium hydrogencarbonate gave the corresponding condensation products.
  • Teruo Matsuura, Masao Kawai, Yasuo Butsugan
    1970 Volume 43 Issue 12 Pages 3891-3894
    Published: 1970
    Released: March 27, 2006
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    The stability of the lactone rings of alkyl substituted coumaran-2,3-diones against hydrolysis and alcoholysis is greatly affected by the positions of alkyl substituents. From UV spectral studies it was suggested that methyl substitutions at positions adjacent to the lactone ring contribute to stability for steric reasons.
  • Teruzo Asahara, Manabu Sen\={o}, Shinsaku Shiraishi, Yoshikazu Arita
    1970 Volume 43 Issue 12 Pages 3895-3898
    Published: 1970
    Released: March 27, 2006
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    Methyl methacrylate polymerized in the presence of a surface active agent in an aqueous system without any ordinary initiators. Anionic surface active agents, such as sodium tetrapropylenebenzenesulfonate and sodium 2-dodecylbenzenesulfonate, markedly effected the polymerization of methyl methacrylate in the presence of water. The polymerization was inhibited by adding hydroquinone to the reaction system and was also affected adversely by oxygen. Water as a reaction medium was found to be indispensable. The polymerization in organic solvents afforded hardly any polymeric products.
  • Kiyotomi Takao, Masami Wayaku, Yuzo Fujiwara, Toshinobu Imanaka, Shiic ...
    1970 Volume 43 Issue 12 Pages 3898-3900
    Published: 1970
    Released: March 27, 2006
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    Catalytic activities of chlorotris(triphenylphosphine)rhodium(I) and rhodium(III) chloride for the oxidation of olefins have been studied. It has been found that the complex and RhCl3 can cause catalytically the oxidation of aliphatic olefins such as styrene, α-methylstyrene or β-methylstyrene to produce carbonyl compounds under oxygen atmosphere. A remarkable solvent effect was observed in the reaction.
  • Hiizu Iwamura, Kaoru Hanaya
    1970 Volume 43 Issue 12 Pages 3901-3908
    Published: 1970
    Released: March 27, 2006
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    The O–H stretching IR absorptions of epimeric 1-tetralols and chroman-4-ols were examined in dilute carbon tetrachloride solutions. The absorption pattern was found to be related to the conformation of the hydroxyl group; the epimers with the quasi-axial OH group showed a singlet νO–H at 3618 cm−1, while those with the quasi-equatorial hydroxyl had doublet absorption at 3622 and 3600 cm−1. Based on these findings 1-tetralol itself was shown to exist preferentially in the OH axial conformation. The bands at 3618 and 3600 cm−1 were assigned severally to the hydroxyl groups bonding to the π-electrons on the benzene ring. When an additional aryl group is present β to the hydroxyl, another O–H···π bonding to the aryl group becomes possible in addition to that between the OH group and the benzene ring of the tetralin and the chroman skeletons. The conformation of the aryl substituents was deduced by applying the empirical correlation relating the geometry of the molecule to the bonded νO–H frequency in a wide variety of aromatic alcohols which incorporate β-arylethanol moiety.
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