Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 47 , Issue 9
Showing 1-50 articles out of 66 articles from the selected issue
  • Sanyo Hamai, Hiroshi Kokubun
    1974 Volume 47 Issue 9 Pages 2085-2088
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    It was found that, like 2-hydroxytriphenylmethanol (HM), 2-hydroxy-4-methoxytriphenylmethanol (HMM) shows photochromism as well as thermochromism. Photo- and thermochromism of HMM occur even in n-hexane, in which a photochemical irreversible reaction occurs for HM. In n-hexane solution of HMM, a three-stage thermal fading pattern was observed at room temperature and at lower temperatures, the pattern becoming a one-stage type at a higher temperature. Mechanical stirring of a sample solution caused a decrease in the concentration of the colored form in n-hexane at room and lower temperatures but not at a higher temperature. These phenomena are caused by the backward reaction on the wall of a sample cell including diffusion as the rate-determining step. In n-hexane–dimethoxyethane (or acetonitrile) mixed solvents, the first-order rate constant becomes smaller with increase in the dimethoxyethane (or acetonitrile) concentration. From a certain concentration, shaking of a cell causes no decrease in the concentration of the colored form.
  • Hiroshi Sugihara, Ling Yuan Chen, Iwao Yasumori
    1974 Volume 47 Issue 9 Pages 2089-2093
    Published: 1974
    Released: March 27, 2006
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    The catalytic activity of X-type zeolite exchanged by Ag+ was studied for the isomerization of 1-butene. The activity gradually increased with the degree of exchange up to ca. 60%, whereafter it rose steeply. A good correlation was found between the activity and the number of acid sites of H0 less than 3.3. Both preferences, that for the formation of cis-2-butene from 1-butene and that for the geometrical isomerization rather than the double bond shift, indicated that the reaction proceeds via a carbonium-ion intermediate formed on an acidic site. In the region of exchange around 40%, however, the cis/trans ratio in the 2-butenes produced was less than unity and a change in the reaction mechanism was suggested. Treatment with H2 enhanced the activity of exchanged zeolite by a factor of 102–103 without any change in the character of the reaction. These results were attributed to the formation of proton-X-zeolite by the replacement of Ag+ with a proton. This conclusion was confirmed by the analysis of deuterium exchange during the isomerization on D2-treated AgX.
  • Masayuki Nakagaki, Noriaki Funasaki
    1974 Volume 47 Issue 9 Pages 2094-2098
    Published: 1974
    Released: March 27, 2006
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    The surface pressure-area curves of mixed monolayers and the equilibrium spreading pressure of solid mixtures were measured at 25 °C for cholesterol and trilaurin as well as tristearin and trilaurin. The phase diagrams of these mixtures were obtained by the measurement of the melting point. From two curves, one representing the relation between the collapse pressure (if the mixed monolayer was not overcompressed) and the composition of mixed monolayer, and the other representing the relation between the equilibrium spreading pressure and the composition of solid mixture, it was shown that the compositions of the mixed monolayer and the solid mixture coexisting in equilibrium were obtained. It was found that when the mixed monolayer of cholesterol and trilaurin was compressed, pure trilaurin began to collapse and deposit, and that the mixed monolayer of tristearin and trilaurin was apt to be overcompressed. It was concluded on the basis of phase rule and thermodynamics for plane interfaces that the equilibrium spreading pressure is constant regardless of the composition of solid mixture if the solid mixture consists of two phases of mixed crystals, and that cholesterol and trilaurin form a regular solution in mixed monolayer.
  • Yasuhiko Shirota, Tamotsu Tomikawa, Takashi Nogami, Kazuhiro Tada, Nao ...
    1974 Volume 47 Issue 9 Pages 2099-2102
    Published: 1974
    Released: March 27, 2006
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    The formation of transient N-vinylcarbazole cation-radical and pyromellitic dianhydride anion-radical was demonstrated for the N-vinylcarbazole-pyromellitic dianhydride-solvent system by means of flash spectroscopy. The transient decay process was found to be solvent-dependent. In 1,2-dichloroethane the decay of the anion-radical was of the first-order at initial stage (t<100 μs), and the second-order kinetics (t<100 μs) then followed. In acetonitrile the transient decay followed the second-order kinetics in the whole time region.
  • Takashi Nogami, Tadanori Hishida, Yasuhiko Shirota, Hiroshi Mikawa, Sa ...
    1974 Volume 47 Issue 9 Pages 2103-2106
    Published: 1974
    Released: March 27, 2006
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    The reaction of o-phenylenediamine with chloranil in ether was studied by measuring visible and ultraviolet absorption spectra at various temperatures between −78 °C and room temperature. Dehydrogenation of o-phenylenediamine by chloranil occurred, o,o′-diaminoazobenzene, 2,3-diaminophenazine and tetrachlorohydroquinone being produced as main reaction products. It was suggested that the reaction involves o-benzoquinone di-imine as an intermediate. For the sake of confirmation, o-benzoquinone di-imine was prepared by an independent method, and its reaction with o-phenylenediamine was examined. The difference in reactivity of isomeric phenylenediamines toward chloranil is discussed.
  • Mahiko Nagao, Kunimitsu Morishige, Toshie Takeshita, Tetsuo Morimoto
    1974 Volume 47 Issue 9 Pages 2107-2110
    Published: 1974
    Released: March 27, 2006
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    The slow reaction of ZnO with CO2 and water in the atmosphere is investigated by following the changes in both the surface area of the structure formed and the amounts of CO2 and water evolved, by heating the product in vacuo at increasingly elevated temperatures. The results obtained show that ZnO reacts extremely gradually with CO2 and water cooperatively in the atmosphere to produce an amorphous surface product with a composition approximate to Zn5(OH)6(CO3)2, and that this product is decomposed by heating in vacuo to release the CO2 and water, leaving a porous structure on the ZnO. The surface area of the product was found to change upon heating: first it increases, passes a prominent maximum value at 200 °C, recovers the original value at 500 °C, and further decreases at higher temperatures; this reflects the initial growth and subsequent destruction of the porous structure. Furthermore, it was confirmed that the destruction of such a honeycomb-like structure is promoted by the adsorption of water.
  • Yutaka Saito, Bak-Kwang Kim, Katsunosuke Machida, Toyozo Uno
    1974 Volume 47 Issue 9 Pages 2111-2114
    Published: 1974
    Released: March 27, 2006
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    The effects of pH on resonance Raman spectra of several hydroxyarylazobenzene-type acid-base indicators have been investigated. All the compounds examined show the azo-type spectra in basic solutions, while the neutral solution spectra are the azo-type for p-hydroxyphenyl compounds and the quinoid-type for α- and β-hydroxynaphthyl compounds. The spectrum of Tropaeoline O changes complicatedly along with the protonation and deprotonation on the pH change.
  • Toshiaki Ohta, Takashi Fujikawa, Haruo Kuroda
    1974 Volume 47 Issue 9 Pages 2115-2120
    Published: 1974
    Released: March 27, 2006
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    The MINDO/2 method was applied to typical molecular complexes such as ammonia–I2, benzene–I2, and benzene–TCNE, these bimolecular systems being treated as single molecules. The intermolecular interaction energy was calculated as a function of intermolecular distance. Stable complex formation with a reasonable stabilization energy was predicted in the ammonia–I2 system. It was predicted in the benzene–I2 system for the axial model, but not for the resting model. However, the stabilization energy for the former was found to be too large. No stable conformation was found in the case of the benzene–TCNE system.
  • Shigeya Niizuma, Yoshiharu Sato, Shiro Konishi, Hiroshi Kokubun
    1974 Volume 47 Issue 9 Pages 2121-2125
    Published: 1974
    Released: March 27, 2006
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    The ESR spectrum of the fluorescein semiquinone radical (dianion form) produced by illumination of an alkaline aqueous solution of uranine and leuco-uranine at pH between 11 and 14 was observed and its hfs constants were determined by comparing the spectrum with those of the mono- and trianion forms of fluorescein semiquinone and those of eosm semiquinone reported by Leaver. Six protons in the xanthene ring were found to be comprised of three pairs of magnetically equivalent protons, which suggests a certain dynamic mechanism to average the coupling constants. From a temperature dependence of the line width, protonation to the –O group followed by deprotonation from the –OH group was proposed as a plausible mechanism.
  • Tooru Atake, Hideaki Chihara
    1974 Volume 47 Issue 9 Pages 2126-2136
    Published: 1974
    Released: March 27, 2006
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    A new adiabatic calorimeter for use with condensed gases from 1.8 K to room temperature has been constructed. The heat capacity of solid and liquid dinitrogen oxide was measured between 1.9 and 184 K together with the vapor pressure above 146 K. The residual entropy was re-evaluated as 6.0 J K−1 mol−1, which is now closer to R ln2, suggesting that the disorder of molecular end-for-end orientation is perfectly frozen in the solid state. The moments of lattice frequency spectrum were derived from low-temperature heat capacities and hightemperature vapor pressures. The anomalous increase of heat capacity below the triple point was interpreted as arising from thermal creation of orientational defects with the enthalpy of formation 10.8 kJ mol−1. Other thermodynamic quantities determined are as follows: triple point of pure N2O 182.407±0.002 K, heat of fusion 6516±20 J mol−1, entropy of fusion 35.7±0.1 J K−1 mol−1, heat of vaporization at 184.81 K and 101.7 kPa 16544±20 J mol−1, normal boiling point 184.74 K, translational zero-point energy 1.6±0.3 kJ mol−1, Debye temperature corresponding to 3N degrees of freedom 141.0±1.0 K.
  • Motomichi Inoue, Ken-ichi Hara, Tatsuo Horiba, Masaji Kubo
    1974 Volume 47 Issue 9 Pages 2137-2140
    Published: 1974
    Released: March 27, 2006
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    The magnetic susceptibilities of tris(2,2′-bipyridine)manganese complexes, [Mn(bpy)3]·2THF and Li[Mn(bpy)3]·4THF (THF: tetrahydrofuran), have been determined over a temperature range of 1.6–320 K. The susceptibility of Li[Mn(bpy)3]·4THF can be explained with a radical ion model, in which three 2,2′-bipyridine radical ions are coordinated to a manganese(II) ion. A similar model is applicable to [Mn(bpy)3]·2THF as well. The presence of antiferromagnetic interaction indicates the formation of a weak covalent bond between manganese and bipyridine. This can be elucidated consistently by the molecular orbital theory.
  • Katsutoshi Ohkubo, Hiroyuki Sakamoto, Kohji Tsuchihashi
    1974 Volume 47 Issue 9 Pages 2141-2145
    Published: 1974
    Released: March 27, 2006
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    A new technique is proposed for estimating the rate constants in systems of linear or nonlinear differential equations, using a polynomial approximation of the observed concentrations of species participating in the reaction and an iterative search technique. The method is implemented by minimizing the errors of the concentrations (of species), as computed by the theoretical equations derived from the linear differential equations or by the trapezoidal averaging simulation, relative to those calculated by the polynomial approximation. The present technique requires the concentrations (at the initial reaction stage) of s-2 species (the s species takes part in the reaction). Two kinetic example, A\ ightleftarrowsB\ ightleftarrowsC and S+E\ ightleftarrowsES→P, have been used to illustrate and develop the present technique.
  • Toshiko Kodama, Shigekazu Kumakura
    1974 Volume 47 Issue 9 Pages 2146-2151
    Published: 1974
    Released: March 27, 2006
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    The 2: 1 complex of pyromellitic dianhydride with trans-4-methylstilbene crystallizes in the Cc space group with four pyromellitic dianhydride molecules and two trans-4-methylstilbene molecules in a unit cell with dimensions of a=12.780, b=7.446, c=15.050 Å, and β=91.09°. In addition to the clearly-defined Laue spots, diffuse streaks elongated perpendicular to the molecular layers were observed with a half period of the b* axis of the reciprocal lattice. The structure was solved from a three-dimensional |E|2 Patterson synthesis and was refined by a block-diagonal least-squares method to the final R value of 0.13 for the visually-estimated 703 reflections. Refinement was difficult, however, because of the large correlation between parameters caused by the disorder. The crystal is built up of molecular layers stacked parallel to the (10\bar2) plane and is disordered in the stacking arrangement of the molecular layers. The pyromellitic dianhydride molecule and one of the benzene rings of the trans-4-methylstilbene molecule are alternately stacked plane-to-plane in infinite columns along [10\bar2]. The ethylene group of the trans-4-methylstilbene molecule joins the two columns. The molecular arrangement of the component molecules resembles those observed in the anthracene, pyrene, and perylene complexes with pyromellitic dianhydride and presents a striking contrast to that of the trans-stilbene complex. The interplanar distances range from 3.25 to 3.56 Å, smaller than that of the trans-stilbene complex.
  • Akihiko Yamagishi, Masahiro Sakamoto
    1974 Volume 47 Issue 9 Pages 2152-2157
    Published: 1974
    Released: March 27, 2006
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    The kinetics of the protonation of sodium salt of 7,7,8,8-tetracyanoquinodimethane (Na+TCNQ\ ewdot) by hydrogen chloride in alcohols and acetonitrile was investigated, using a stopped-flow apparatus. In methanol, the protonation rate is first-order in HCl and second-order in Na+TCNQ\ ewdot, while in ethanol, the rate is one-half-order in HGl and second-order in Na+TCNQ\ ewdot. The protonation rate in acetonitrile is first-order in HCl, but it deviates from second-order in Na+TCNQ\ ewdot. These results are interpreted in terms of the rapid formation of a protonated intermediate in the initial stage of the reaction, according to TCNQ\ ewdot+H+\ ightleftharpoonsHTCNQ\ ewdot The reversibility of this reaction is well demonstrated by the second-order dependence of the rate on Na+TCNQ\ ewdot. The rate is also compared with the protonation rate of semiquinones, such as sodium salts of p-chloranil and 2,3-dicyano-l,4-benzoquinone, from the view point of the difference in reactivity between carbon and oxygen acids.
  • Masuzo Nagayama, Osamu Okumura, Seiji Noda, Hiroshi Mandai, Akira Mori
    1974 Volume 47 Issue 9 Pages 2158-2161
    Published: 1974
    Released: March 27, 2006
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    The rates for the sulfonation of 1-dodecene with the sulfur trioxide–dioxane complex were measured spectrophotometrically. A bimolecular process occurred in this reaction, the rate being proportional to [1-dodecene] [SO3-dioxane]. Furthermore, the stereochemistry of the initial products of the sulfonation reaction between cis or trans-2-butene and the sulfur trioxide-dioxane complex was studied. An equimolar amount of sulfur trioxide–dioxane (1 : 1) was added to cis- or trans-2-butene in chloroform to give the sultone, (I) or (II); (I) 1.5(q), 4.7–5.1 (m), JAB 7.9, JBC 8.0, JCD 6.0 Hz; (II) 1.5(q), 4.2–4.6(m), JAB 6.8, JBC 5.4, JCD 6.8 Hz. These results indicate that the 2,3-butanesultones were produced stereospecifically from the corresponding 2-butene isomers. Similarly, the sulfonation of cis- or trans-2-pentene with sulfur trioxide-dioxane gave the corresponding 2,3-pentanesultones.
  • Hiroshi Kudo, Terutomi Mogi, Kiyoshi Hoizumi
    1974 Volume 47 Issue 9 Pages 2162-2165
    Published: 1974
    Released: March 27, 2006
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    1,1,1-Trifluoro-2-chloro-2-bromoethane labeled with 82Br (fluothane-82Br) was purely separated from neutron-irradiated fluothane by means of a gas-chromatographic technique. The maximum radiochemical yield of fluothane-82Br was 38.3% when the target material was irradiated with neutrons to nvt of 3.4×1016 n·cm−2. Of the many organic species produced by the recoil events following the radiative neutron capture and subsequent (I.T.) processes, CF382Br and CF3CHBr82Br were also identified. In order to elucidate the mechanism of recoil labeling, the scavenger effects were examined in the CF3CHClBr–Br2 system, Br2 being used as a radical scavenger. The “high-energy” yields of CF3CHCl82Br thus estimated were approximately 3.6 to 4.8%. It was suggested that most of the 82Br-labeled species were formed through the “thermal” processes including the reaction of 82Br with the organic radicals produced by the radiolysis of the parent fluothane.
  • Yoshiaki Hidaka, Tsuyoshi Kataoka, Masao Suga
    1974 Volume 47 Issue 9 Pages 2166-2170
    Published: 1974
    Released: March 27, 2006
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    The ignition of ethylene-oxygen mixtures highly diluted with argon was studied in a shock tube by monitoring the emission from CH* and C2* or OH*. The measurements covered the temperature range of 1400–2100 K at the C2H4/O2 ratios of 0.33–1.00. From the observation of the CH*, C2*, and OH* emissions, a mechanism for the production of chemiluminescent species upon ethylene oxidation was briefly discussed, and from the observation of the induction period of the CH* emission, the following equation was found:
    logτ_CH[O_2]=-11.45+27.5×10^3/4.58T
    in units of s mol l−1, the rate-determining step being C2H3+O2→C2H3O+O.
  • Kiyoshi Okazaki, Rei Yugeta, Ken-ichi Kowari, Shin Sato
    1974 Volume 47 Issue 9 Pages 2171-2173
    Published: 1974
    Released: March 27, 2006
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    The G-values of nitrogen from the gas-phase γ-radiolysis of the C3-hydrocarbons (propane, propylene, and cyclopropane) in the presence of nitrons oxide have been measured at the temperatures from −35 to 150 °C. The G-values increased with an increase in the pressure of N2O and were saturated at about 4 mol% of N2O. The saturated values, G(N2)max’s showed characteristic temperature dependences. In propane, they scarcely changed with the temperature and stayed at around 2 Ge. Here Ge is the G-value of electrons estimated from the W-value of the hydrocarbon. In propylene, the G(N2)max changed from Ge at −35 °C to about 2 Ge at 150 °C, while in cyclopropane it changed from Ge at −35 °C to 4.5 Ge at 100 °C. Possible reaction mechanisms to explain these results have been discussed.
  • Shin Sato, Kiyoshi Okazaki, Shin-ichi Ohno
    1974 Volume 47 Issue 9 Pages 2174-2180
    Published: 1974
    Released: March 27, 2006
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    The binary-encounter collision theory has been applied to the calculation of the G-values for the ionization and excitation of noble gases irradiated by 100 keV electrons. The G-values obtained were as follows in the order of He, Ne, Ar, Kr, and Xe: 2.27, 2.19, 2.81, 3.20, 3.45 for G(electrons), 0.85, 1.55, 1.92, 1.64, 1.51 for G(singlet states), and 0.17, 0.07, 0.13, 0.23, 0.39 for G(triplet states). The method of the calculation and the significance of the results were discussed.
  • Toshio Uchijima, Yukio Yoneda
    1974 Volume 47 Issue 9 Pages 2181-2185
    Published: 1974
    Released: March 27, 2006
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    Kinetic studies have been carried out on the heterogeneous decomposition of hydrogen peroxide over several nickel oxide catalysts calcined at different temperatures. Kinetic parameters such as reaction order and apparent activation energy depend somewhat on the reaction conditions, but show practically no change with catalyst. The catalytic activity changes with calcination temperature, becoming minimum at 550 °C and maximum at 600 °C. The trend does not change with pretreatment of the catalyst, resembling the behavior of surface excess oxygen having a relatively higher oxidation power. Thus the distribution of oxidation power is closely related to catalytic activity for the decomposition of hydrogen peroxide. We therefore applied the regional analysis assuming that the surface excess oxygen represents active sites for catalysis, and a specific regional activity corresponds to each regional oxygen. It was found that the fifth region (the range of free energy change of adsorption of oxygen being from −11.1 to −12.6 kcal/mol) markedly contributes to the reaction rate, and the calculated rates agree with the observed ones. The nature of the active site was discussed as regards pretreatment of the catalyst.
  • Yoshinori Hasegawa
    1974 Volume 47 Issue 9 Pages 2186-2188
    Published: 1974
    Released: March 27, 2006
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    The interactions of m-dinitrobenzene and 1-substituted 2,4-dinitrobenzenes with sodium methoxide in meth-anolic dimethyl sulfoxide were studied with a rapid scan spectrophotometer. A similar study of 1-substituted 2,4-dinitrobenzenes with sodium hydroxide in aqueous dimethyl sulfoxide was carried out. Except for a few cases, the first transient colored-complexes of 3-substituted 2,6-dinitrocyclohexadienates were observed at initial stages before the complete formation of second colored-complexes having the π-electronic structures of 1,3-dinitropentadienyl anion.
  • Manabu Sen\={o}, Kazutoshi Iwamoto, Teruzo Asahara
    1974 Volume 47 Issue 9 Pages 2189-2191
    Published: 1974
    Released: March 27, 2006
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    Using a twin-type calorimeter, the enthalpy changes of solutions and reactions with aqueous KCN solution of Zeise’s salts, K[PtCl3(olefin)], were measured. As ligand olefins, ethylene, propylene, 1-butene, 1-pentene, and 1-hexene were employed. It was estimated from a thermochemical analysis that the order of strength of platinum-olefin bonding is as follows; K[PtCl3(C3H6)]\gtrsimK[PtCl3(C3H6)]\gtrsimK[PtCl3(1-C6H12)]\gtrsimK[PtCl3(1-C4H8)]\gtrsimK[PtCl3(1-C5H10)]. This order was compared with the data of infrared spectra and both the results coincide with each other.
  • Michio Sorai, Teruo Nakamura, Syûzô Seki
    1974 Volume 47 Issue 9 Pages 2192-2196
    Published: 1974
    Released: March 27, 2006
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    The heat capacity of a low-temperature liquid crystal EBBA (N-p-ethoxybenzylidene-p′-butylaniline) of 99.75% (mol) purity was measured in the range 14–375 K with an adiabatic calorimeter. The melting point Tm was 305.62 K, and the enthalpy and entropy of fusion 27.09 kJ mol−1 and 88.71 J K−1 mol−1, respectively. The temperature of mesomorphic transition Tc from nematic to isotropic liquid was 349.08 K, and the enthalpy and the entropy changes due to the mesomorphic transition were 1.553 kJ mol−1 and 4.524 J K−1 mol−1, respectively. Excess heat capacity due to the mesophase transition, C(excess), is represented by C(excess)∼ε−0.7 in the range 10−4<ε<10−1.5, where ε≡|TTc|⁄Tc. This implies that the mesomorphic transition of EBBA can be regarded as of critical phenomena, characterized by a second-order rather than a first-order nature.
  • Hitoshi Ohtaki, Masunobu Maeda
    1974 Volume 47 Issue 9 Pages 2197-2199
    Published: 1974
    Released: March 27, 2006
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    The structure of hydrated copper(II) ion was determined by means of the X-ray diffraction of a 3.55 M copper(II) perchlorate solution. The radial distribution curve showed that the copper(II) ion has a distorted octahedral structure with six water molecules. Four water molecules occupy the equatorial sites of the octahedron at a distance of 1.94±0.02 Å from the Cu(II) ion and the other two water molecules at the axial sites are 2.43±0.03 Å distant from the central ion.
  • Mutsuo Kodama
    1974 Volume 47 Issue 9 Pages 2200-2202
    Published: 1974
    Released: March 27, 2006
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    The kinetics of the substitution reactions of DTPA with N-(2-hydroxyethyl)iminodiacetate (HIDA) and N-(2-hydroxyethyl)ethylenediamine-N,N′,N′-triacetate (EDTA-OH) complexes of nickel(II) and EDTA-OH and 2,2′-ethylenedioxydi(ethylamine)-N,N,N′,N′-tetraacetate (GEDTA) complexes of cobalt(II) were studied systematically by employing the polarographic technique. The reaction of ethylenediaminetetraacetate (EDTA) with the nitrilotriacetate (NTA) complex of nickel(II) in an alkaline medium was also studied. All the substitution reactions were found to have a common reaction mechanism. They were first-order with respect to DTPA or EDTA and also first-order with respect to the 1:1 ratio metal (II) complex of HIDA, NTA, EDTA-OH, or GEDTA. From a comparison of the observed rate constants with those estimated on the basis of the proposed reaction intermediate, the detailed reaction mechanism and the steric effect of the DTPA anion on the reaction rates were studied. The DTPA anion had practically no effect on the rates of the substitution reactions of the aminopolycarboxylate complexes of metal (II) ions.
  • Isao Yoshida, Hiroshi Kobayashi, Keihei Ueno
    1974 Volume 47 Issue 9 Pages 2203-2207
    Published: 1974
    Released: March 27, 2006
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    In connection with the purification of metal chelates by zone refining, thermal properties of the following β-diketone chelates of tervalent cobalt(III), aluminum(III), iron(III), manganese(III), and chromium(III) were investigated by differential thermal analysis (DTA). The β-diketones used in this study were heptane-3,5-dione, nonane-4,6-dione, 2,6-dimethylheptane-3,5-dione, 2,8-dimethylnonane-4,6-dione, 2,2,6,6-tetramethylheptane-3,5-dione, and tridecane-6,8-dione. Metal chelates of the alkyl substituted pentane-2,4-diones showed a lower melting- and higher decomposition temperature in comparison with the pentane-2,4-dionates. Discussion is given on the effects due to the structures of the alkyl substituents upon thermal properties of the hexacoordinate metal chelates.
  • Makoto Chikira, Hiroshi Yokoi, Taro Isobe
    1974 Volume 47 Issue 9 Pages 2208-2212
    Published: 1974
    Released: March 27, 2006
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    The ESR spectra of triplet-state dimers have been obtained for various bidentate and quadridentate salicylaldehyde Schiff base complexes of copper(II) in frozen solutions. The spectra have been analysed on the basis of the previously-obtained results concerning the non-coaxial g and fine-structure tensors. The results indicate that the angles between the g|| axis and the copper-copper axis of the dimers for the quadridentate Schiff base complexes are considerably smaller than those for the bidentate ones. Each of the actually-measured ESR spectra, however, consisted of two mutually-overlapping spectra; one is due to dimers (M2), and the other, to monomers (M). The equilibrium constant for 2M\ ightleftharpoonsM2 has been estimated by comparing the ESR spectral intensities of the two species. The factors which govern the dimer formations have been discussed in some detail.
  • Isamu Kawasuji, Akiko Sato, Shin Suzuki
    1974 Volume 47 Issue 9 Pages 2213-2216
    Published: 1974
    Released: March 27, 2006
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    Europium (II) was found to be an excellent reductant for reducing protactinium in microquantities to the tetravalent state. The behavior of Pa(IV) in the perchloric acid solution was investigated by the TTA-benzene extraction method. It was found that the PaOH3+ ion existed predominantly in a 0.03–3 M perchloric acid solution at the ionic strength of 3. The reaction of TTA extraction may proceed as:
    &PaOH^3++4HA=PaA_4+H_2O+3H^+
    \intertextor
    &PaOH^3++4HA=Pa(OH)A_3(HA)+3H^+
    The distribution ratio of Pa(IV) in the system using Eu(II) as the reductant is about ten times as large as that in the system using Cr(II) as the reductant. It was considered that a non-extractable complex may be formed between Pa(IV) and Cr(III), while such a complex may not be formed when Eu(II) is used as the reductant.
  • Hitoshi Ohtaki, Masunobu Maeda, Satoshi Ito
    1974 Volume 47 Issue 9 Pages 2217-2221
    Published: 1974
    Released: March 27, 2006
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    X-Ray diffraction measurements were carried out for aqueous solutions of cadmium perchlorate and sodium tetraiodocadmate. X-Ray scattering data showed that the hydrated Cd2+ ion is coordinated to six water molecules, the distance between Cd2+ and H2O being 2.31±0.02 Å, and that the CdI42− complex has a tetrahedral configuration with a Cd–I distance of 2.79±0.01 Å. The tetrahedral structure of the CdI42− complex was confirmed by Raman spectroscopy.
  • Kazuyoshi Tanaka, Kunio Nakano
    1974 Volume 47 Issue 9 Pages 2222-2225
    Published: 1974
    Released: March 27, 2006
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    The rigorously derived equation for a catalytic current was applied to the evaluation of the rate constant for the oxidation reaction of bis(2,2′-bipyridine)copper(I) by nitrite ion by use of a computer and subroutine program for the curve-fitting method. This method made it possible to calculate the rate constant from low limiting current in the presence of nitrite ion. The rate in acetate buffer solutions has first-order dependence on each reactant and hydrogen ion, and the apparent rate constant is 1×106 M−2 s−1 at 25 °C.
  • Osamu Matsumoto, Michio Saito, Takashi Yoshino
    1974 Volume 47 Issue 9 Pages 2226-2228
    Published: 1974
    Released: March 27, 2006
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    The formation of cubic molybdenum carbide (α-MoC1−x) by the carbonization of MoO3 with graphite by heating with argon plasma arc was studied. α-MoC1−x including a small amount of hexagoanl η-MoC1−x. was formed. By the carbonization of mixture of MoO3 and TiO2 with graphite, a cubic solid solution of Mo–Ti–C system was formed. Chemical and X-ray analyses showed that the cubic form is defective in carbon content. The density of the cubic form was in agreement with that determined by means of X-ray diffraction. The products were found to be superconductors, the transition temperature varying with composition. The highest transition temperature 11.7 K was obtained for Mo0.95TiO0.05C0.75.
  • Masunobu Maeda, Hitoshi Ohtaki, Georg Johansson
    1974 Volume 47 Issue 9 Pages 2229-2237
    Published: 1974
    Released: March 27, 2006
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    The structures of the AuCl4 and the AuBr4 complexes in aqueous solutions have been determined from X-ray scattering measurements on concentrated solutions of tetrachloroauric and tetrabromoauric acids. Both the tetrachloroaurate(III) and the tetrabromoaurate(III) complexes were found to have a square planar symmetry. The values obtained for the interatomic distances within the complexes are: Au–Cl, 2.291 Å; cis-Cl–Cl, 3.24 Å; trans-Cl–Cl, 4.58 Å; Au–Br, 2.432 Å; cis-Br–Br, 3.44 Å; trans-Br–Br, 4.86 Å.
  • Kohei Ametani
    1974 Volume 47 Issue 9 Pages 2238-2241
    Published: 1974
    Released: March 27, 2006
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    Atomic absorption spectrophotometric studies were carried out on single-crystal rare-earth magnetic garnets, (R1R2)3(Fe,Ga)5O12, where R1 and R2 are Y, Eu, Gd, and Er, and sulfides RCr3S6, where R is Y, Gd, Dy, Ho, and Er. A method using lanthanum chloride to suppress the interference effects of other elements was demonstrated for the atomic-absorption determination of rare earths. Lanthanum chloride is much better than alkaline metal chlorides (NaCl, KCl, and CsCl) and chelating agents (EDTA·2Na and EDTA·2NH4) for removing the interference effects of foreign elements from the yttrium measurement. Similar results with lanthanum chloride are observed with other rare earths. Experimental results for various samples are also presented. The present method has been utilized for several years in our laboratories to analyse rare earths in newly prepared materials.
  • Kazuyoshi Seguchi, Akira Sera, Kazuhiro Maruyama
    1974 Volume 47 Issue 9 Pages 2242-2246
    Published: 1974
    Released: March 27, 2006
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    The effect of pressure on the Diels-Alder reaction was investigated. The observed activation volume was found to have a significant correlation with the activation free energy of the reaction. A correlation diagram between the activation volume and the activation free energy was proposed. By this diagram, the position of the transition state in the Diels-Alder reaction was discussed, and the activation volume was suggested to be a good diagnostic probe for the position of the transition state. The importance of the contribution of the volume contraction resulting from secondary orbital interaction to the apparent activation volume was pointed out.
  • Naomichi Furukawa, Toshiaki Masuda, Masatoshi Yakushiji, Shigeru Oae
    1974 Volume 47 Issue 9 Pages 2247-2250
    Published: 1974
    Released: March 27, 2006
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    The reactions of dialkyl and alkyl aryl N-p-tosylsulfilimines with hydroxide or methoxide in methanol afforded either S-substitution products or Pummerer type products or a mixture of both, their distribution being dependent on the structure of the sulfilimine. From the results of analyses, the mechanisms of the formation of these products are discussed. A similar alkaline methanolysis of sulfonium ylides was also investigated.
  • Toshihiro Okada, Yoshiki Okamoto, Hiroshi Sakurai
    1974 Volume 47 Issue 9 Pages 2251-2254
    Published: 1974
    Released: March 27, 2006
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    The chlorophosphonation of toluene, p-xylene, ethylbenzene, and diphenylmethane gave methyldiphenylmethanes; 2,4′,5-trimethyldiphenylmethane and ethyl-1,1-diphenylethanes; and p-benzyltriphenylmethane respectively as the main products. Isopropylbenzene gave α-methylstyrene, 4-methyl-2,4-diphenylpentene-1, 4-methyl-2,4-diphenyIpentene-2, and 1,1,3-trimethyl-3-phenylindane, in addition to the ordinary chlorophosphonated products. Those diphenylmethane derivatives may be formed by the electrophilic attack of the benzylic cations, presumably resulting from electron transfer from the benzylic radicals to phosphorus trichloride with the participation of the oxygen or oxy radical, upon toluene, p-xylene, ethylbenzene, or diphenylmethane. α-Methylstyrene may be formed by the elimination of a proton from the intermediate 1,1-dimethylbenzyl cation, resulting from isopropylbenzene in a manner similar to that above. Diphenylpentene and phenylindane derivatives may be formed by the acid-catalyzed dimerization of α-methylstyrene.
  • Yoshiro Ogata, Katsuhiko Takagi
    1974 Volume 47 Issue 9 Pages 2255-2259
    Published: 1974
    Released: March 27, 2006
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    Irradiation of four 1-aryl-1,2-propanediones (Ia–Id) with over 300 nm light in 2-propanol gives reduction products identified to be the corresponding pinacols or hydrols formed by the reduction at the aroyl (but not acetyl) oxygen. The products from 1-(o-tolyl)-1,2-propanedione (Id) can also be accounted for by the initial hydrogen abstraction from ortho methyl by the aroyl carbonyl oxygen. Their photoreactivities are discussed as regards their electronic emission spectra and triplet configuration.
  • Hitomi Suzuki, Osamu Yagiu, Terukiyo Hanafusa
    1974 Volume 47 Issue 9 Pages 2260-2263
    Published: 1974
    Released: March 27, 2006
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    Products obtained by the reaction of the title compounds with fuming nitric acid in dichloromethane were investigated. Decamethylbiphenyl gave 6,6′-bis(nitrooxymethyl)-2,2′,3,3′,4,4′,5,5′-octamethylbiphenyl or 2,6,6′-tris(nitrooxymethyl)-2′,3,3′,4,4′,5,5′-heptamethylbiphenyl as the major product, depending on the amount of nitrating agent. 2,3,4,5,6-Pentamethyl-2′,3′,4′,5′,6′-pentachlorobiphenyl similarly gave 6-nitrooxymethyl-2,3,4,5-tetramethyl-2′,3′,4′,5′,6′-pentachlorobiphenyl or 2,6-bis(nitrooxymethyl)-3,4.5-trimethyl-2′,3′,4′,5′,6′-pentachlorobiphenyl. Some plausible reaction sequences for the exclusive ortho attack on the alkyl side-chains of biphenyl systems have been suggested.
  • Shizen Sekiguchi, Katsuo Shinozaki, Tetsuo Hirose, Kohji Matsui, Kiyos ...
    1974 Volume 47 Issue 9 Pages 2264-2266
    Published: 1974
    Released: March 27, 2006
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    The intermediates in the reaction of 1-(N,N-dimethylamino)-2,4-dinitronaphthalene (9) with sodium methoxide have been studied in the mixtures of DMSO and CH3OH. The NMR spectra of the equimolar mixture of 9 and sodium methoxide indicate that 9 and a 1,1-disubstituted Meisenheimer complex coexist immediately after mixing, and that nearly all 9 changed into the Meisenheimer complex 15 min after mixing. The addition of 2 mol of sodium methoxide to 1 mol of 9 gave no 1,1,3,3-tetrasubstituted 2,4-dinitronaphthalene Meisenheimer complex. 1-Piperidino- or 1-(N-methyl-N-n-butylamino)-2,4-dinitronaphthalene reacted with sodium methoxide to give a similar Meisenheimer complex.
  • Tadahiro Wakui, Yoshio Otsuji, Eiji Imoto
    1974 Volume 47 Issue 9 Pages 2267-2271
    Published: 1974
    Released: March 27, 2006
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    The reactions of 2-substituted 2-bromodimedones with various bases were studied. The behavior of the dimedones changed with the base and substituent attached to the dimedones. Treatment of 2-alkyl-2-bromodimedones (1a and 1b) with a weak nucleophilic base such as sodium acetate afforded 2-alkyl-4,4-dimethyl-2-cyclopenten-1-ones (2a and 2b), 2-alkyl-5,5-dimethyl-3-oxo-1-cyclopentene-1-carboxylic acids (3a and 3b), 2-alkyl-5,5-dimethylcyclohexane-1,3-diones (4a and 4b) and carbon monoxide. A similar treatment of 2,2-dibromodimedone (7) with the weak nucleophilic base gave 2,3-dibromo-4,4-dimethyl-2-cyclopenten-1-one (8), 2-bromo-5,5-dimethylcyclohexane-1,3,4-trione (9) and 2-bromodimedone (10). However, the reactions of 1a and 7 with a strong nucleophilic base such as sodium ethoxide gave mainly the open-chain products, ethyl 3,3-dimethyl-5-oxoheptanoate (5a) and diethyl 3,3-dimethylglutarate (11). On treatment of 1a with silver acetate, a debrominative dimerization occurred to produce the dimer 6. The mechanisms of these reactions were discussed.
  • Kazuko Takahashi, Shunsuke Takenaka, Yoriko Kikuchi, Kahei Takase, Tet ...
    1974 Volume 47 Issue 9 Pages 2272-2276
    Published: 1974
    Released: March 27, 2006
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    Attempt was made to dehydrogenate p-(3,4-diphenyl-1,3-cyclopentadien-1-yl)phenyltropilidene, prepared by treating p-tropylphenyllithium or p-tropylphenylmagnesium bromide with 3,4-diphenylcyclopent-2-enone, to 3″, 4″-diphenyl-1- cycIoheptatrienylidene-4-cyclopentadienylidene-2,5-cyclohexadiene, 10,11-diphenyl [5.6.7]quinarene. The resulting blue pigment showed spectral properties in line with those of p-(3,4-diphenyl-1,3-cyclopentadien-1-yl)phenyltropylium ion, [5.6.7]quinarenium ion, carrying a delocalized positive charge (VII’) but not those of expected cross-conjugated hydrocarbon.
  • Chikahiko Eguchi, Akio Kakuta
    1974 Volume 47 Issue 9 Pages 2277-2282
    Published: 1974
    Released: March 27, 2006
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    The isomerization among c-L-Hyp-L-Hyp (1), c-L-Hyp-D-aHyp (2) and c-D-aHyp-D-aHyp (3) has been examined in ethanolic sodium ethoxide at 25–78 °C as well as in aqueous solutions at 75–250 °C. At equilibrium state, 1 was predominant and 2 was not found at all in the reaction mixture. By the use of this isomerization reaction and the difference of solubility between 1 and 3, 3 could be converted almost quantitatively to 1. The mixture of 1 and 3 was obtained in good yield directly from D-aHyp or L-Hyp by heating in water or ethylene glycol. 1 was hydrolyzed quantitatively to L-Hyp by acid. Thus, L-Hyp was obtained with the yield of 59% from D-aHyp by combination of preparation, isomerization and acid hydrolysis of cyclic dipeptide.
  • Hiroshi Hirota, Takahiko Tsuyuki, Yoshiaki Tanahashi, Takeyoshi Takaha ...
    1974 Volume 47 Issue 9 Pages 2283-2286
    Published: 1974
    Released: March 27, 2006
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    Lupan-3-one (5) was irradiated in n-hexane under an argon atmosphere using a high pressure mercury lamp. Besides three seco compounds, namely 10α-(2-formylethyl)-5β-isopropenyl-des-A-lupane (6), 10α-(2-carboxyethyl)-5β-isopropyl-des-A-lupane (8), and 10α-(2-carboxyethyl)-5β-isopropenyl-des-A-lupane (9), two seco-nor compounds, 10α-(carboxymethyl)-5β-isopropyl-des-A-lupane (7) and lactone of 10α-(carboxymethyl)-5α-hydroxy-5β-isopropyl-des-A-lupane (10), have been isolated and their structures have been determined. NMR signals of 10 were examined using Eu(fod)3-d27 as a shift reagent.
  • Norio Kobayashi, Akiko Osawa, Tamotsu Fujisawa
    1974 Volume 47 Issue 9 Pages 2287-2291
    Published: 1974
    Released: March 27, 2006
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    Polydithiocarbamates have been synthesized by the polycondensation of di-K or di-Na bisdithiocarbamates based on secondary diamines with bischloromethylated aromatics in N,N-dimethylformamide. The polymers obtained in good yields had inherent viscosities up to 0.66. The polymers derived from 1,3-di-4-piperidylpropane were soluble in organic solvents, such as dichloromethane and chloroform, and gave transparent, tough films from the solution. These polymers decomposed upon UV irradiation, with the liberation of carbon disulfide. The photopolymerization of methyl methacrylate in the presence of the polymer has also been studied.
  • Tateaki Wakamiya, Tadashi Teshima, Ichiro Kubota, Tetsuo Shiba, Takeo ...
    1974 Volume 47 Issue 9 Pages 2292-2296
    Published: 1974
    Released: March 27, 2006
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    γ-Hydroxy-β-lysine is a new basic amino acid isolated from the hydrolyzates of antitubercular peptides, tuberactinomycin A and N. In order to confirm the structure and establish the stereochemistry of the amino acid, two diastereoisomers of γ-hydroxy-DL-β-lysine were synthesized by Arndt-Eistert synthesis via β-hiydroxyornithine. Synthetic erythro and threo isomers were found to be identical spectroscopically and chromatographically with the corresponding forms obtained from the antibiotics respectively.
  • Frieder W. Lichtenthaler, Peter Voss, Gerd Bambach
    1974 Volume 47 Issue 9 Pages 2297-2303
    Published: 1974
    Released: March 27, 2006
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    Four-step syntheses for the 4′-arnino-4′-deoxy-β-D-glucopyranosyl nucleosides of adenine (7), uracil (12) and cytosine (16) from a readily accessible galactose derivative (2) are described, in overall yields of 41–47%. The reaction sequence, used, involved (i) stannic chloride catalyzed nucleosidations of 2 with the bis-trimethylsilyl derivatives of N6-benzoyladenine, uracil and N4-acetylcytosine, (ii) displacement of the 4′-sulfonyloxy groups in 3, 10, and 15 by azide, (iii) de-O-benzoylation and (iv) hydrogenation. An alternate route to 12 and 16, comprising nucleosidation of tetraacetyl-4-acetamido-4-deoxy-D-glucopyranose (20) via the classical Hilbert-Johnson approach proved feasable, yet inferior with respect to yields and accessibility of educts. The structures and configurations assigned followed from the synthetic route as well as from spectroscopic data, particularly from the acetyl resonances of the peracetylated nucleosides 9, 14, and 18, which are in excellent agreement with those of the respective glucosyl- and 3-acetamido-3-deoxy-glucosyl analogs (Table).
  • Frieder W. Lichtenthaler, Tamio Ueno, Peter Voss
    1974 Volume 47 Issue 9 Pages 2304-2310
    Published: 1974
    Released: March 27, 2006
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    In a four step sequence from 1-O-acetyl-2,3,6-tri-O-benzoyl-4-O-mesyl-α-D-glucose (4), 4′-amino-4′-deoxy-β-D-galactosyl-cytosine (1) was synthesized, involving stannic chloride catalyzed nucleosidation with bis(trimethylsilyl)-N4-acetyl-cytosine, azidolysis of the 4′-sulfonyloxy group, deblocking and reduction (overall yield: 48%). An alternate, though preparatively less satisfactory approach was used for the preparation of the uracil analogue 2, which started from β-D-glucosyl-cytosine or uracil (9 or 15) and proceeded via standard blocking and deblocking reactions to the 4′-O-mesylglucosyl-uracil (20) and was concluded by azidolysis (20, 21), removal of protecting groups and reduction. Structural and configurational assignments evolved from the mode of preparation as well as from spectroscopic data, most conveniently from the acetyl resonances of the peracetylated nucleosides 8 and 24, which are in accord with those of their galactosyl and 3-acetamido-3-deoxy-galactosyl counterparts (Table).
  • S. M. Verma, O. Subba Rao, K. O. P. Sinha
    1974 Volume 47 Issue 9 Pages 2311-2314
    Published: 1974
    Released: March 27, 2006
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    A series of N′,N′-disulphonyl and N′-sulphonyl-N′-acetyl derivatives of N-amino-9,10-dihydroanthracene-9,10-endo-α-methyl-α,β-succinimide and N-amino-1,2,3,4-tetrahydro-1,4-etheno/ethano-naphthalene-2,3-exo/endo-dicarboximides with a benzo ring in the cage-moiety were prepared and their NMR spectra were studied. Shielding constants of the substituents provide evidence for the non-eclipsed conformations of the N′-substituents with the ring carbonyls. The preferred conformations of N′-sulphonyl-N′-acetyl derivatives are explained on steric grounds. In N′-tosyl-N′-acetyl derivatives the tosyl group takes up a fixed conformation about N′-SO2 bond in which the aryl part of the tosyl group projects away from the cage-moiety.
  • Alpana Ghatak, Arati Das, Subir Kr. Roy
    1974 Volume 47 Issue 9 Pages 2315-2318
    Published: 1974
    Released: March 27, 2006
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    Complex dielectric permittivities in ortho- and para-bromoanisoles and β-bromophenetole in the liquid state have been measured in 1.6, 3.17, and 3.49 cm microwave regions at different temperatures. The dielectric data were analysed in terms of molecular and intramolecular relaxation times. The values of methoxy group relaxation times and its contribution to total polarization obtained in the liquid bromoanisoles have been compared to the corresponding values in dilute solutions reported in literatures. Activation energy for dielectric relaxation and viscous flow in all the cases have also been obtained in all the liquids.
  • W. R. Bansal, S. Puri, K. S. Sidhu
    1974 Volume 47 Issue 9 Pages 2319-2320
    Published: 1974
    Released: March 27, 2006
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    Evidence is presented to show that excited O2(1∑g+, 1Δg) is an intermediate in the dye (methylene blue, rose bengal, eosin) sensitized oxidation of diphenylamine which yeilds N-phenyl-p-benzoquinonimine. The relative rates in different solvents are reported and a mechanism is suggested.
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