Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 44 , Issue 4
Showing 1-50 articles out of 83 articles from the selected issue
  • Satoshi Morimoto
    1971 Volume 44 Issue 4 Pages 879-884
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Heats of mixing ΔHM at infinite dilution and integral heats of dilution ΔHd were directly measured for the systems of atactic polystyrenes (PSt: MW≤104, prepared by Pressure Chemical Co.) with benzene, toluene, and chloroform. The results are summarized as follows: (1) ΔHM and ΔHd decrease remarkably with the molecular weight of PSt in all solvents used. (2) The glass energies of the samples treated under the same thermal conditions were investigated and the large difference of heat capacities between liquid and glassy state of PSt was observed in the low molecular weight region. (3) Schulz’s theory of osmotic second virial coefficient of athermal polymer solutions was found to agree, to a good approximation, with the differential heat ‾ΔH1 of dilution in toluene in the molecular weight region between 103 and 104. (4) The NMR and the X-ray diffraction analyses were performed for the PSt oligomer liquid (MW 600). All alkyl end group of molecules and an order formation in the liquid were observed. They are discussed in terms of calorimetric data.
  • Susumu Tajima, Nobuhide Wasada, Toshikazu Tsuchiya
    1971 Volume 44 Issue 4 Pages 884-887
    Published: 1971
    Released: March 27, 2006
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    A part of the mass spectra for derivatives of aniline and anisole was interpreted using the results of MO calculation. Compounds studied were: aniline derivatives: o-, m-, and p-compounds of anisidine, aminophenol, chloroaniline, nitroaniline, aminobenzoic acid, and aminoaeetophenone; and anisole derivatives: o-, m-, and p-compounds of anisidine, methoxyphenol, chloroanisole, nitroanisole, methoxyben zoic acid, and methoxybenzaldehyde. The intensities of certain fragment ions in the mass spectra of these compounds were compared with the results of simple LCAO MO calculation for these compounds. A simple relation was found between the intensity and the partial bond order for a frontier electron of the bond ruptured.
  • Yo-ichiro Mashiko, Takako Shinoda, Hisae Enokido
    1971 Volume 44 Issue 4 Pages 888-893
    Published: 1971
    Released: March 27, 2006
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    An apparatus of differential thermal analysis has been designed and constructed for the purpose of determining the purity of organic compounds with as small an amount of sample as possible, within a short time and yet with an accuracy of better than ±0.001 mol%. Degussa platinum thermometers were used. They were calibrated with a precision of better than ±0.004° against a standard platinum resistance thermometer. Methods for determining the impurities in samples on the basis of irreversible thermodynamics have been developed. The results were compared with those obtained by using an adiabatic calorimeter of our laboratory and by the National Bureau of Standards. The apparatus proved to be useful in determining the purity of about 1 ml of samples, whose melting points lie in the temperature range −200°C–+200°C within an accuracy of ±0.004 mol% in about 1.5 hr.
  • Hideshi Hattori, Shun-itsu Miyashita, Kozo Tanabe
    1971 Volume 44 Issue 4 Pages 893-895
    Published: 1971
    Released: March 27, 2006
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    The distribution of Brönsted and Lewis acidities of nickel sulfates heat-treated at various temperatures in air or in a vacuum has been determined by observing the infrared spectra of pyridine adsorbed on the sulfates in the range 1300–1600 cm−1. It has been found that the Brönsted acidity increases with the rise of temperature of heat treatment in air, attains a maximum value at 250°C and then decreases, while the maximum of the Lewis acidity appears at a higher temperature (about 400°C), the sum of both acidities giving the total acidity measured by n-butylamine titration method. An experiment in a vacuum showed that Lewis acid is converted into Brönsted acid by the addition of water. The structural nature and the catalytic activity of the Brönsted and Lewis acid sites on nickel sulfate are discussed.
  • Hiroshi Kawabe, Masaya Yanagita
    1971 Volume 44 Issue 4 Pages 896-901
    Published: 1971
    Released: March 27, 2006
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    The amination of chloromethylated polystyrene with 2-aminobutanol in dioxane was studied. The apparent rate constatns, kapp, as computed by the simple second-order equation, were found to increase linearly with the degree of amination; this was in contrast with the amination with n-butylamine, in which the kapp decreased as the amination proceeded. By assuming that the reactivity of the chloromethyl group is enhanced when it is situated next to the already-aminated group as a result of the “hydrophilic effect” of the hydroxyl group, rate equations which give the elementary rate constants were derived. In the presence of a large excess of amine, the over-all kinetics can be expressed by:
    dx⁄dt=[ab⁄(3k1k2)][3k1(k1k2)e−3k1at+2k1k2ek2at]
    where x is the concentration of chloride ions at time t; where a is the initial concentration of amine, and b, that of the chloromethyl group, and where k1 and k2 are the rate constants of the elementary reactions which are independent of the neighboring group and under the influence of it respectively. The values of kapp calculated on the basis of k1 and k2 were also found to agree with the observed values.
  • Soji Tsuchiya, Isao H. Suzuki
    1971 Volume 44 Issue 4 Pages 901-907
    Published: 1971
    Released: March 27, 2006
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    Simultaneous measurements of Na D and CO fundamental emissions have been made behind a shock wave in CO–Ar or CO–N2–Ar mixture containing a trace of Na vapor. The relaxation of a population in each vibrational level is calculated by use of Montroll-Shuler equation. The Na D emission intensity behind the shock wave in the 1.5% CO+Ar mixture nearly follows the relaxation of CO molecules excited to a vibrational level v=3 or 4, which is energetically lower than the 32P state of Na. This means that most Na atoms are excited by collisions with CO molecules in a level higher than v=3, and that the Na D reversal temperature exceeds the vibrational temperature of CO molecules behind the shock wave. In contrast to this, excitation of Na behind the shock wave in the 1.7% CO+49.3% N2+49.0% Ar mixture is due to collisions with N2 molecules in a level higher than v=6, and a nearly resonant vibrational-to-electronic energy transfer is realized. The relative values of the exciting rate kve by collisions with CO or N2 in a level v are determined to be k1e :k2e :k3e k4e :k5e=<0.01 : 0.04: 1 : 1.6 : <2 for Na–CO and k4e :k5e :k6e :k7e :k8e=<0.03 : 0.21 : 1 : 1.4 : <2 for Na–N2 collisions at about 2600°K.
  • Yasuo Ueno, Isamu Sano
    1971 Volume 44 Issue 4 Pages 908-911
    Published: 1971
    Released: March 27, 2006
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    An aqueous NaCl solution (10%) containing a surface active substance was dispersed to a mist with a Dautrebande type atomizer. The influence of the surface active substance on the droplet size and mass concentration of the mist during aging was studied. We examined ethyl alcohol, acetic acid, ethyl acetate, acetone, glycerine, and a commercial nonionic surfactant. From the results it was found that at an early stage of aging, the droplet number present in mist was inversely proportional to the fourth power of droplet size.
  • Yoshito Onishi
    1971 Volume 44 Issue 4 Pages 912-915
    Published: 1971
    Released: March 27, 2006
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    To clarify the reaction mechanism of catalytic oxidation of hydrogen on titanium dioxide, the rate of catalytic oxidation of hydrogen by oxygen and the reduction rate of titanium dioxide by hydrogen have been measured by a static method in temperature range of 400–650°C at 10−2 mmHg. The results were compared with those of carbon monoxide which were reported in the previous papers. The oxidation reactions of hydrogen on anatase and rutile were first order with respect to hydrogen and independent of the oxygen pressure. The oxidation rate was almost the same as the reduction rate of titanium dioxide by hydrogen. The activation energy was 29.2 kcal/mol for anatase and 17.8 kcal/mol for rutile, and the difference between these values for two crystal forms was nearly equal to that of the oxidation of carbon monoxide. Therefore, it may be considered that the mechanism of oxidation of hydrogen is analogous to that of carbon monoxide. The electric conductivity of the catalyst during the oxidation of hydrogen was larger than that in oxygen at the same temperature, and was still larger than that during the oxidation of carbon monoxide except for a few cases on anatase. There were close correlations between the electric conductivity and the amount of active oxygen of the catalyst and the reduction rate constant of titanium dioxide by both hydrogen and carbon monoxide.
  • Masahiro Hatano, Osamu Ito
    1971 Volume 44 Issue 4 Pages 916-923
    Published: 1971
    Released: March 27, 2006
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    The charge-transfer bands of the loose complexes between Group IV tetrahalides (chlorides and bromides) and methylbenzenes were observed, and the electron affinities of these tetrahalides were systematically evaluated from these observed charge-transfer bands. The semi-empirical molecular orbital calculations (the extended Hiickel method) for these tetrahalides revealed that the tetrahalides interact with the benzene ring using the vacant molecular orbital involving the empty d atomic orbital of the halogen atom in the tetrahalides. Moreover, the meanings of the electron affinities estimated in this study were discussed in terms of the molecular orbitals, by comparing them with the values of the electron affinities evaluated by other methods.
  • Tsutomu Kagiya, Y\={u}z\={o} Sumida, Takeshi Watanabe, Toshihiro Tachi
    1971 Volume 44 Issue 4 Pages 923-928
    Published: 1971
    Released: March 27, 2006
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    An infrared spectroscopic study of the hydrogen-bonding interaction of binary solvents (S1–S2) with trimethylsilanol has been made, where CCl4 is used as S1 and the aromatic hydrocarbons and the O- and N-containing solvents, as S2. On the basis of the findings on the O–H frequency shifts (ΔνOH) of trimethylsilanol, the equilibrium constants (K) and the preferential coordination constants (α1−2) of hydrogen-bond formation, the difference in the O–H···π and the O–H···n hydrogen-bonding interactions has been discussed. The free-energy changes (−ΔG) were found to be better related to the apparent half-widths (Δν1⁄2) of the O–H bands than the ΔνOH. The ΔνOH of trimethylsilanol caused by the interaction with the solvent was in good correlation with the donor number defined as the heat of mixing of the solvent with antimony(V) chloride. From the linear relationship between the ΔνOH of trimethylsilanol and the ΔνSOH of the surface silanol caused by the gas-phase adsorption on silica gel, it was also found that the proton-donating power of the surface silanol was considerably larger than that of trimethylsilanol and was nearly equal to that of p-nitrophenol. There existed a linear relationship through the point of origin between the α1−2 and the separation factors (αS1−2) in the liquid-phase adsorption on the silica gel surface.
  • Yasuyoshi Okada, Kazumi Nakatsu, Akira Shimada
    1971 Volume 44 Issue 4 Pages 928-933
    Published: 1971
    Released: March 27, 2006
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    The crystals of 3,4-furandicarboxylic acid dimethylester are monoclinic of the space group P⁄21a, with unit cell dimensions a=12.64, b=8.16, c=7.97 Å, and β=100.0°. An approximate structure was determined by application of the symbolic addition phase determining procedure. After several cycles of least-squares refinement, the discrepancy index for the 901 observed reflections was reduced to 14%. In the molecule the furan ring is planar, and one carbomethoxy group is almost on the same plane as the furan ring, while the other makes an angle of 10.5° with the ring. The bond lengths and angles do not differ appreciably from the values found in the other compounds, except for those of C(3)–C(4)=1.41 Å, C(4)–C(3)–C(6)=131° and C(3)–C(4)–C(7)=132°, the latter two being larger than normal values probably because of interaction between the carbonyl-oxygens. The mode of packing of the molecules and a scheme of twinning found in this crystal is discussed.
  • Tetsuo Miyazaki, Takahisa Yamada, Terunobu Wakayama, Kenji Fueki, Zen- ...
    1971 Volume 44 Issue 4 Pages 934-937
    Published: 1971
    Released: March 27, 2006
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    The effects of CCl4 on the formation of H2 and C4H9 radicals in the radiolysis of i-C4H10 have been studied in glass at 77°K and the liquid at 195°K. The yield of H2, which is not affected by the addition of N2O or SF6, decreases sharply upon the addition of CCl4 in the glass, as in the crystal (This Bulletin, 42, 1164 (1969); 43, 1017 (1970).), while it does not so sharply decrease in the liquid as in the solid. The effects of CCl4 on the yields of H2 correspond fairly well to those on the yields of the C4H9 radicals. The effects of CCl4 in the glass are explained by the excitation transfer from the excited butane molecule to CCl4, as in the radiolysis of i-C4H10 in the crystal. A kinetic treatment suggests that its mechanism may be the exciton transfer. Some remarks on the primary process of ionization in the radiolysis of solid hydrocarbons are given from the viewpoint of exciton transfer.
  • Masashi Tanaka, Jiro Tanaka
    1971 Volume 44 Issue 4 Pages 938-944
    Published: 1971
    Released: March 27, 2006
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    The electronic structures and spectra of thymine, uracil, and their derivatives have been studied by measuring the electronic absorption spectra of the single crystals. In the polarized absorption spectra of the crystal, an unusual absorption band appears at about 285 mμ in the tail of the usual π→π* transition when the crystal has the C=O···H–N-type hydrogen bond. The direction of the transition moment of this band is found to be along the direction of the hydrogen bond between a pair of C=O···H–N-groups, the nature of which is discussed from several viewpoints. The direction of the transition moment of the first and second π→π* bands is determined to be inclined at about +38° and +86° from the C4···N1 line toward the C5 atom. The result for the first band is not in perfect agreement with the finding of Stewart and Davidson regarding 1-methylthymine, who regarded this angle as either −14° or +19°.
  • Takuzo Funabiki, Kimio Tarama
    1971 Volume 44 Issue 4 Pages 945-951
    Published: 1971
    Released: March 27, 2006
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    The hydrogenation of butadiene catalyzed by pentacyanocobaltate(II) was studied in water and in glycerol-methanol-water and ethylene glycol-methanol solutions. The amount of hydrogen absorbed, and the rate of hydrogen absorption, in the water solvent were much greater than in the other solvents. The composition of the butenes produced by the hydrogenation in the water solution was trans-2->>1->cis-2-butene at CN/Co<5.1, and 1->>trans-2->cis-2-butene at CN/Co>5.1; this composition was affected by the concentration of the complex. The composition of the butenes produced in the glycerol-methanol solution was trans-2->>1–>cis-2-butene at CN/Co<5.4 and 1->cis-2->>trans-2-butene at CN/Co>5.4; a concentration effect similar to that in the water solution was observed. The composition of butenes in the glycerol-methanol-water solution at CN/Co=6.0 was remarkably affected by the composition of the solvent. In the ethylene glycol-methanol solution, cis-2-butene was much more producible than in the glycerol-methanol solution. The mechanism of the hydrogenation of butadiene by pentacyanocobaltate(II) was discussed on the basis of these solvent effects on the composition of products, and on the basis of the kinetical behavior of this hydrogenation reaction.
  • Yasumasa J. I’haya, Tomoyasu Nakamura
    1971 Volume 44 Issue 4 Pages 951-957
    Published: 1971
    Released: March 27, 2006
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    The absorption spectra, optical rotatory dispersion, and circular dichroism (CD) of the DNA- and RNA-thionine complexes were measured at the nucleic acid phosphate to dye ratios (P/D) 0.01–50 and at the temperature range 20–85°C. The Cotton effects of P/D >3 complexes were observed in the wavelength region 520>680 nm, being resolved at least into four partial Cotton effects. From their transient profiles with changing P/D values and the observed temperature effect, they were interpreted to be induced from the dye monomers bound near the asymmetric environment of nucleic acids. The Cotton effects of P/D <2 complexes in the wavelength region 450–580 nm are new and have not been reported for other DNA-dye systems. The trough of these Cotton effects completely disappeared at 50°C and the decreasing profile of its relative rotation with increasing temperature was roughly parallel to that of the dimer fraction. The newly developed Cotton effects are inferred to result from an interaction between the dye dimers aggregated in a helical fashion along the nucleic acid helices. The negative sign CD maximum observed in the wavelength region 300–330 nm is probably due to DNA-dye interactions, but its origin is not clear.
  • Yoshio Matsunaga, Gunzi Saito
    1971 Volume 44 Issue 4 Pages 958-963
    Published: 1971
    Released: March 27, 2006
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    The electronic structures of about sixty polycrystalline molecular complexes of benzidine and its derivatives have been examined on the basis of the vibrational and electronic spectra. The complexes show a strong tendency to be non-ionic, in spite of the low ionization potentials of the electron donors. Several non-ionic complexes exhibiting resistivities of the order of 103–105 ohm cm have been found. The optical and electrical properties of the complexes consisting of donor molecules with amino groups and of acceptor molecules with carbonyl groups are distinctly different from those of the others. The first charge-transfer absorption band of the solid complex in the former group appears at an energy considerably lower than that of the corresponding complex in chloroform. Moreover, the activation energy for semiconduction seems to be appreciably reduced by the formation of a hydrogen bond.
  • Koichi Niihara
    1971 Volume 44 Issue 4 Pages 963-967
    Published: 1971
    Released: March 27, 2006
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    Samarium hexaboride was prepared by the borothermal reaction; 2 Sm2O3+(6+4x)B=4 SmBx+3 B2O2. The residual oxygen content amounted to less than 0.03 w/o under optimum reaction conditions heating at 1650°C for 2 hr under a high vacuum. It was found by X-ray intensity and density measurements that the samarium hexaboride stayed stable over a large nonstoichiometric region from Sm0.68B6 to SmB6. These extensive nonstoichiometric properties of samarium hexaboride can be explained in terms of the required electron numbers of the SmB6 network in hexaboride.
  • Keizo Suzuki, Masao Tsuchiya
    1971 Volume 44 Issue 4 Pages 967-970
    Published: 1971
    Released: March 27, 2006
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    The effect of pressure on the association of rhodamine B (RB) and methylene blue (MB) in water has been investigated on the basis of their absorption spectra under hydrostatic pressures up to 4500 atm at room temperatures. Pressure increases the association of these dyes. The volume changes accompanying the 2 monomer\ ightleftarrowsdimer process are calculated. The values are −10.4 cc/mol and −10.6 cc/mol in RB and MB respectively. These negative values are inconsistent with the suggestions by Rohatgi and Singhal and by Mukerjee and Ghosh that hydrophobic bonds are responsible for the associations of RB and MB. It is more plausible to assume that the hydrogen bond is the main binding force in the dye associations. London’s dispersion force and the increase in the dielectric constant of water with the increase in the pressure may also assist the dye associations.
  • Hiroshi Fujimoto, Shinichi Yamabe, Kenichi Fukui
    1971 Volume 44 Issue 4 Pages 971-974
    Published: 1971
    Released: March 27, 2006
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    The importance of the charge-transfer interaction from the highest occupied (HO) molecular orbital (MO) of a donor to the lowest unoccupied (LU) MO of an acceptor molecule has been stressed on the basis of the numerical results of the calculation on a model of the SN2 reaction of methyl chloride. The effect of a counter ion on the frontier orbitals has been discussed. For the E2 reaction of ethyl chloride, it has been discussed how the orienting effect of the leaving nucleophile is transmitted to the trans-β-hydrogen by means of the frontier electron density. The influence of the rotation about the Cα–Cβ bond upon the reactivity of β-hydrogen has also been discussed.
  • Shoji Hiroma, Haruo Kuroda, Hideo Akamatu
    1971 Volume 44 Issue 4 Pages 974-977
    Published: 1971
    Released: March 27, 2006
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    The results of a preliminary investigation on the semiconductive and photoconductive behaviors of the TCNQ crystal are described. The single crystal of TCNQ shows a resistivity of the order 1011 Ω·cm at room temperature with an activation energy of about 0.6 eV. The photoconductive sensitivity of a TCNQ crystal is comparatively high. There are two types of crystal with respect to sensitivity to visible light. In both cases, the low-energy tail is extended up to about 1.5 eV. It is shown that both the activation energy of photoconduction and the light-intensity dependence of photocurrent differ appreciably in visible and ultraviolet regions.
  • Takeshi Takemura, Kiyoaki Hara, Hiroaki Baba
    1971 Volume 44 Issue 4 Pages 977-984
    Published: 1971
    Released: March 27, 2006
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    Triplet–triplet (T–T) absorption spectra of naphthalene, α- and β-methoxynaphthalene have been observed in rigid-glass solutions at 77°K by the rapid-scan spectrophotometric method and in fluid solutions at room temperature by the flash spectroscopic method. Hydrogenbonding effects on the T–T absorption spectra were examined for α- and β-naphthol. α-Naphthol was found to give different absorption spectra, depending upon the solvents employed. In a certain case the spectrum is attributed to a photoproduct rather than to the triplet state of a-naphthol. Analysis of the spectral data leads to the conclusion that the T–T absorption spectra in α-derivatives involve two different electronic transitions, and those in β-derivatives are due to a single electronic transition which is analogous to the transition in naphthalene. In agreement with these observations, calculations performed by the Pariser-Parr-Pople method predict that in the low-energy region, α-naphthol should have two allowed and detectable transitions, 3Ψ13Ψ7 and 3Ψ13Ψ8, and naphthalene and β-naphthol have only one such transition, 3Ψ13Ψ9. The wave functions of triplet states are subjected to configuration analysis, with the result that 3Ψ7 and 3Ψ8 of α-naphthol are related predominantly to 3Ψ8 and 3Ψ9 of naphthalene, respectively.
  • Tetsuo Miyazaki, Yoshiteru Fujitani, Terunobu Wakayama, Kenji Fueki, Z ...
    1971 Volume 44 Issue 4 Pages 984-988
    Published: 1971
    Released: March 27, 2006
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    The main gaseous products in the radiolysis of solid succinic acid are CO2, CO, and H2. It was found that the G(CO+H2) from the powder is much higher than that from the single crystal, while there is no difference in G(CO2) between the powder and the single crystal, indicating that CO2 is produced homogeneously in the solid. The clear difference in the G(CO+H2) between the powder and the single crystal cannot be attributed to the analytical procedure, the secondary reaction of CO, or the presence of H2O as an impurity. It may be due to the difference in the primary process of the radiolysis. It is conceivable that the mobile active entity formed by the γ-irradiation of the crystal migrates to the special reaction sites and produces CO and H2. The difference in G(CO+H2) may also be due to the different numbers of the sites between the powder and the single crystal. It is discussed whether the mobile entity is a cation, an electron, or an exciton.
  • Keniti Higasi, Yoshinori Koga, Masahiko Nakamura
    1971 Volume 44 Issue 4 Pages 988-992
    Published: 1971
    Released: March 27, 2006
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    There are four Debye equations for dilute solutions which can be used to determine the relaxation time of a polar solute molecule. This paper offers a critical examination of these equations, especially two representative formulas which are mutually independent. If the solute molecule has a non-rigid configuration and has two relaxation times, τ1 and τ2, for overall and internal rotations, respectively, average relaxation times will be obtained from these equations based on measurements at a single frequency. However, the analysis of this paper shows that under a certain condition (if a proper frequency for the measurement and a suitable equation for the calculation are employed) one may make a crude estimate regarding one of the two relaxation times. Further, the ratio of two relaxation times seems to afford a clue for investigating the mechanism of internal rotation. In addition, Cole-Cole dispersion and atomic polarization problems are also discussed.
  • Kazuo Chitoku, Keniti Higasi, Masahiko Nakamura, Yoshinori Koga, Hiroa ...
    1971 Volume 44 Issue 4 Pages 992-997
    Published: 1971
    Released: March 27, 2006
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    This paper gives details of the equipment and the method of the measurement at 100 GHz. Dielectric constants and losses are measured at this frequency for ten organic molecules in benzene and four (aniline, phenol, and its derivatives) both in benzene and in dioxane. A majority of the molecules studied are of non-rigid configuration. Discussion is given of the relaxation times and the mechanism of internal rotation involved. Hydrogen bonding effects in aniline, phenol, and its derivatives are also discussed.
  • Kenji Kubo, Kazuyoshi Ogino
    1971 Volume 44 Issue 4 Pages 997-1000
    Published: 1971
    Released: March 27, 2006
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    Second virial coefficients for polystyrene (PS), poly-p-chlorostyrene (PPCS), and poly-o-chlorostyrene (POCS) were determined in various solvents by osmotic-pressure measurements. Free-energy parameters, χ, were estimated from the values of the second virial coefficients. It was shown that the values of χ in each solvent at 30°C became larger in the following order: PS, POCS, PPCS in toluene; PS, PPCS, POCS in chlorobenzene; PPCS, PS, POCS in n-butyl acetate. It was indicated that, in addition to the effect of intermolecular forces, another parameter related to the stiffness of the polymer chains should be considered in order to discuss the thermodynamic properties of polymer solutions. It was shown that the values of χ for two polychlorostyrenes in n-butyl acetate increased with an increase in the temperatures, unlike the behavior of PS in the same solvent.
  • R. J. Tykodi
    1971 Volume 44 Issue 4 Pages 1001-1003
    Published: 1971
    Released: March 27, 2006
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    A simple heat conduction example is used to show that the choice of boundary conditions for describing a steady process, although of no consequence in the linear current-affinity region, governs the applicability (or the lack thereof) of various thermodynamic assertions to the non-linear current-affinity region. The need for a whole family of classificatory principles to aid us in organizing our knowledge about steady processes is pointed out.
  • N. Chattanathan, C. Kalidas
    1971 Volume 44 Issue 4 Pages 1004-1006
    Published: 1971
    Released: March 27, 2006
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    The activity coefficients of the molecular forms of a few nitrodiphenylamine indicators were determined by a solubility method in basic solutions of ethylene and propylene glycols. The medium effects on the ions of these indicators were also obtained by determination of the medium effects of their molecular forms separately by solubility measurements. Variation of the activity coefficients and the medium effects on the ions of the indicators are discussed.
  • Ryokai Shirakawa, Shiro Takeda, Takao Umegaki, Taijiro Okabe
    1971 Volume 44 Issue 4 Pages 1007-1010
    Published: 1971
    Released: March 27, 2006
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    An electrochemical investigation was made on the corrosion reaction of iron in phosphatizing solution to clarify the mechanism of the formation of phosphate coating. Polarization characteristic curves revealed the corrosion of iron to be under cathodic control implying that the formation of phosphate coating occurs thus under cathodic control. The corrosion rate increased considerably by the addition of KNO3 or KNO2 which is used as an accelerator in phosphatization. The formation of phosphate coating was much accelerated by cathodic polarization of iron, but repressed by anodic polarization and rotation of the iron electrode.
  • Masaoki Oku, Kichinosuke Hirokawa
    1971 Volume 44 Issue 4 Pages 1010-1013
    Published: 1971
    Released: March 27, 2006
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    Some metal solid samples were burned in a nitrogen plasma flame, and the spectrum intensity-time curves were spectrographically observed. The curves indicated that the fractional distillation of alloying elements was caused by the reactions of the solid-alloy sample and nitrogen gas. The fractional distillation was explained in terms of the difference in the stabilities of the metal nitrides. The distribution of the emission species and the temperature of the flame suggested that there were few chemical reactions in the flame or that the chemical reactions in the flame had little effect on the spectrum intensities. In an appendix, the method of line-pair selections for obtaining the correct temperature is considered.
  • Takashi Omori, Shaw-Chii Wu, Takanobu Shiokawa
    1971 Volume 44 Issue 4 Pages 1014-1017
    Published: 1971
    Released: March 27, 2006
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    Thermal annealing reactions of 57Co formed by the EC and β+-decay of the 57Ni-labeled hexamminenickel(II) halide complexes were investigated in detail by means of ion-exchange techniques. When the annealing is carried out at high temperatures, the chemical behavior of 57Co is remarkably affected by the thermal decomposition of the parent and daughter complexes. In the intrinsic annealing, however, the annealing curves have characteristic shapes and the plateau yields of 57Co(NH3)63+ ion are independent of the temperature, depending on the nature of the outer-sphere anion. The unusual oxidation reaction of the recoil 57Co(II) species is explained by the action of the crystal defects in the near-neighborhood of the recoil site.
  • Goro Wada, Noriko Yoshizawa, Yoko Sakamoto
    1971 Volume 44 Issue 4 Pages 1018-1024
    Published: 1971
    Released: March 27, 2006
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    The formation constants K1 and K2 of the complexes Fe(NCS)2+ and Fe(NCS)2+ in dimethyl sulfoxide (DMSO) and the rate constants and the activation parameters of the electron transfer reaction between Fe(II) and Fe(III) in DMSO catalyzed by thiocyanate ion were measured. K1 and K2 are (8.4±0.9)×102 M−1 and (0.97±0.10)×102 M−1 at μ=0.1 M and 25°C, respectively. The apparent rate constant kapp is nearly independent of acid concentrations and increases markedly with total thiocyanate ion concentration. The rate constants k1and k2 of Fe2+-Fe(NCS)2+ and Fe2+-Fe(NCS)2+ systems are (2.24±0.35)×102 M−1sec−1 and (2.96±0.64)×103 M−1 sec−1 at μ=0.2 M and 25°C, respectively. ΔH1\ eweq=8.9±1.0 kcal/mol and ΔS1\ eweq=−17±3 cal/deg·mol are obtained from the temperature dependence of kapp. From a comparison with the data of cases catalyzed by Cl and SCN ions in water and DMSO, the present electron transfer reaction is deduced to proceed probably via the inner-sphere mechanism with the SCN ion as a bridging ligand, similar to the Cl ion-catalyzed reaction in DMSO.
  • Eiichi Miki, Soto-o Kubo, Kunihiko Mizumachi, Tatsujiro Ishimori, Hisa ...
    1971 Volume 44 Issue 4 Pages 1024-1027
    Published: 1971
    Released: March 27, 2006
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    The 15NO-complexes for K3[Mn(CN)5(NO)]·2H2O, K3[Mn(CN)5(NO)] and Ag2[Mn(CN)5(NO)] were prepared. By measuring and calculating the effect of the nitrogen isotope 15N on the infrared spectra, the Mn–N–O arrangement was found in all the complexes, and the absorption bands due to the skeletal vibrations between the manganese and the NO group were clearly assigned.
  • Niro Matsuura, Masahito Yoshimura, Masao Takizawa, Yukio Sakaki
    1971 Volume 44 Issue 4 Pages 1027-1030
    Published: 1971
    Released: March 27, 2006
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    The formation of hypophosphate and phosphate in the radiolysis of a phosphite solution was established by the anion-exchange chromatographic technique. The quantitative determination of their yields was made by colorimetry of the phosphate and hypophosphate with the Mo(V)+Mo(VI) reagent, which develops molybdenum-blue colors in two steps at different temperatures. The G values in an aerated condition are 0.01 molecules/100 eV in acid and 0.1 molecule/100 eV in neutral pH with respect to the hypophosphate formation, independent of the phosphite concentration. In a deaerated system much higher values are obtained, amounting to around 0.5 molecules/100 eV at a phosphite concentration of 10−3 M. The G values of hypophosphate plus phosphate are around 3.0; this is in agreement with the half-value of the primary radical yields, 1/2·(gred+gOH), reported in the data derived from the radiation-chemical studies in the aqueous system. The hypothesis that the hypophosphate (IV) ion radical is a transient species in the oxidation of phosphite to phosphate is supported by the results obtained in this work.
  • Tong-Chuin Pung, Toyoaki Kato, Yoshinaga Oka
    1971 Volume 44 Issue 4 Pages 1031-1034
    Published: 1971
    Released: March 27, 2006
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    A method for the determination of zirconium has been studied by activation analysis with bremsstrahlung photons, with molybdenum used as the internal-reference element. This method is based on the γ-ray spectrometric measurement of the 89Zr activity produced by the 90Zr(γ,n) reaction and on the comparison of this activity with the 88Zr activity formed by the (γ,α) reaction on molybdenum. The reaction products and their rates of production in zirconium and in molybdenum have also been examined as functions of bremsstrahlung maximum energies up to 60 MeV, and the best conditions for the determination of zirconium are proposed. When the maximum energy was set at 20 MeV, no interfering reactions occurred; under the present experimental conditions, a zirconium content down to about 18 μg can be determined accurately. The reliability and the versatility of this method are demonstrated.
  • Kashiro Kuroda, Kiyokatsu Watanabe
    1971 Volume 44 Issue 4 Pages 1034-1039
    Published: 1971
    Released: March 27, 2006
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    A series of cobalt(III) complexes containing the tetradentate ethylenediamine-N,N′-diacetate anion (EDDA) and chloride, water, ammonia, ethylenediamine, 1,10-phenanthroline, and 2,2′-dipyridyl as the ligands occupying the residual coordination positions have been prepared, and some of their physical and chemical properties have been examined. Two isomers have been isolated in the cases of the phenanthroline and dipyridyl complexes; they have been inferred to be the α-cis(pink) and the β-cis(red) isomers on the basis of their electronic absorption spectra. A new convenient route for the preparation of the series has been presented, a route which passes through the dichloro, chloroaquo, and diaquo complexes.
  • Tomihito Kambara, Minoru Hara
    1971 Volume 44 Issue 4 Pages 1040-1043
    Published: 1971
    Released: March 27, 2006
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    It was found that dithizone in an aqueous alkaline solution shows sharp AC polarographic peaks; the indirect determination of mercury by means of these peaks was investigated. After the extraction of mercury(II) dithizonate into benzene, the excess dithizone was eliminated. Then the mercuric ion was stripped into the aqueous phase containing the iodide ion. The isolated dithizone in the benzene layer was back-extracted into the alkaline supporting electrolyte solution and the polarogram was recorded. By the present method, up to 30 μg of mercury can be determined.
  • Kenichi Akiba, Nobuo Suzuki
    1971 Volume 44 Issue 4 Pages 1043-1047
    Published: 1971
    Released: March 27, 2006
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    Addition compound formation between uranyl bis-thenoyltrifluoroacetonate (UO2A2) and tributyl phosphate(S) was studied by a partition method, using uranium-237 as the tracer. The formula of the adduct complex was shown to be UO2A2·S. The solvent effect on the adduct formation constant was taken into account in connection with the activity; the activity coefficients of each species in various solutions were calculated from the molar volume and the solubility parameter. The formation constants based on the molar fraction, Kx, in a number of solvents were pre-estimated, employing logKx=7.08 in carbon tetrachloride as a reference. They are in agreement with the observed values. The formation constant in terms of activity was found to be constant logKS°=5.77±0.30. A correlation between the formation constants of the two adducts, UO2A2·S and ZnA2·S, was demonstrated.
  • Luciano Caglioti, Angelo G. Giumanini
    1971 Volume 44 Issue 4 Pages 1048-1050
    Published: 1971
    Released: March 27, 2006
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    The synthesis of a linear azoalkene, α-phenylazostilbene (1), not conjugated to strong electron withdrawing groups is reported. α-(p-Methoxyphenylazo)stilbene (3) was prepared by a direct method. The mass spectra of 1 and 3 showed a rearrangement yielding positive ions of benzonitrile and benzaldehyde anils (7).
  • Fumio Toda, Nobuhiro Ooi, Katsuhiko Akagi
    1971 Volume 44 Issue 4 Pages 1050-1054
    Published: 1971
    Released: March 27, 2006
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    The reaction of the title compound (I) with mercuric halide in an aprotic and in a protic solvent afforded the fulvene derivative (VII) and the dihydrofuran derivative (VIII or IX) respectively. Both the cross-reactions (bromo-analog of I (Ia)+HgCl2, chloro-analog of I (Ib)+HgBr2) in an aprotic solvent afforded the chloro-fulvene derivative (VIIb). However, when the above reactions were carried out in a protic solvent, the product was the dihydrofuran derivative (IX), in which the halogen combining with carbon is chlorine and that combining with mercury is bromine. On the basis of the results of those cross-reactions, the reaction mechanism will be discussed. Acetonitrile showed distinctive behavior. In acetonitrile, the bromine of Ia was easily exchanged with the chlorine of sodium chloride at room temperature, and Ib was obtained quantitatively.
  • Shuzo Akiyama, Masazumi Nakagawa, Kichisuke Nishimoto
    1971 Volume 44 Issue 4 Pages 1054-1062
    Published: 1971
    Released: March 27, 2006
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    During the course of studies on the spectral regularities of linear conjugated systems bearing aromatic terminal groups (cf Tetrahedron Lett., 1964, 719; ibid., 1968, 1121; This Bulletin, 39, 2320 (1966); ibid., 40, 340 (1967)), we found that the free electron model (FEM) cannot explain the effect of substitution on the electronic spectrum of phenanthrene. In order to get further information the electronic spectra of forty-eight phenanthrene derivatives each bearing a substituent at 2-, 3-, or 9-positions have been examined, and it was found that the electronic spectra of these derivatives also cannot be explained on the basis of FEM. SCF-MO-CI calculation has been carried out on phenanthrylpoly-ynes and hydroxyphenanthrenes revealing that the discrepancy between the observation and the expectation from FEM in the behavior of La and Lb of phenanthrene derivative is attributable to a complex configuration interaction.
  • Takao Yoshida, Kaoru Harada
    1971 Volume 44 Issue 4 Pages 1062-1067
    Published: 1971
    Released: March 27, 2006
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    Several organic acids which contain C=O, C=N, and C=C double bonds are catalytically hydrogenated in the presence of various optically active organic bases by the use of several solvent systems. Effects of bases and solvents on the optical activities of the products are examined.
  • Kaoru Harada, Kazuo Matsumoto
    1971 Volume 44 Issue 4 Pages 1068-1071
    Published: 1971
    Released: March 27, 2006
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    Optically active α-amino acids were synthesized from azomethines of N-α-ketoacyl-amino acid esters by catalytic hydrogenation. When optically active (S)-alanine was used, (R)-amino acyl-(S)-alanine ester was obtained. When alkyl groups of optically active (S)-amino acids in the N-α-ketoacyl-amino acid esters were larger than ethyl group, the configurations of newly formed amino acids were found to be (S). From these results possible steric courses of the asymmetric syntheses are discussed.
  • Shigeaki Nakamura, Kazuaki Kawamoto
    1971 Volume 44 Issue 4 Pages 1072-1078
    Published: 1971
    Released: March 27, 2006
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    In order to investigate whether or not the dehydrogenation activity of the reduced copper is affected by ultraviolet light, the reaction of such alcohols as ethanol, 1-propanol, 2-propanol, and 1-butanol was carried out with reduced copper and ultraviolet light at 250°C. It was found that the conversion of alcohols and the yield of aldehydes were larger with the reduced copper under ultraviolet light than without the light, and that aldol condensation for the ethanol reaction was recognizable when the reduced copper catalyst was used without ultraviolet light.
  • Sigeru Torii, Hideo Tanaka, Hitosi Ogo, Siro Yamasita
    1971 Volume 44 Issue 4 Pages 1079-1084
    Published: 1971
    Released: March 27, 2006
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    Anodic oxidation of 5-alkyl-2-furoic acids (4 and 10) in protic solvents has been studied. The major products were 1-butenolides (12, 13, 16, and 17) and γ-keto esters (11 and 15) and their acids (14 and 18). Methyl 5-n-hexyl-2,5-dimethoxy-2,5-dihydro-2-furoate 19 was converted into γ-keto ester 11 and its acid 14 by hydrolysis with alkali and into 1-butenolide 12 by electrolysis of the alkaline solution. A possible mechanism of the anodic oxidation of 5-alkyl-2-furoic acids has been discussed.
  • Mitsuaki Narita, Takero Teramoto, Makoto Okawara
    1971 Volume 44 Issue 4 Pages 1084-1089
    Published: 1971
    Released: March 27, 2006
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    The reverse Diels-Alder reaction of N-substituted maleimide adducts of furan is a useful method for the preparation of N-substituted maleimides which can not be obtained by the direct dehydration of maleamic acids owing to the formation of the corresponding isomaleimides. O-Benzyl, O-acetyl, O-benzoyl, O-benzenesulfonyl, and O-methyl-N-hydroxymaleimide adducts of furan decompose at 140–190°C to produce the corresponding maleimides. The homo- and co-polymerization with styrene of these maleimides were carried out and monomer reactivity ratios and Q-e values for these maleimides were determined. The copolymer obtained were converted to the copolymer of N-hydroxymaleimide and styrene.
  • Takashi Matsumoto, Kenji Fukui
    1971 Volume 44 Issue 4 Pages 1090-1095
    Published: 1971
    Released: March 27, 2006
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    The Reformatsky reaction of 2-methyl- or 2-ethylcyclohexanone with ethyl bromoacetate gave a mixture of epimeric alcohols, which were then separated by column chromatography in an 80 : 20 ratio. The configurations of these major and minor products were identified as ethyl trans- and ethyl cis-2-methyl (or ethyl)-1-hydroxycyclohexylacetate respectively on the basis of their IR analyses, their chromatographic behavior, and correlation with the products of the Grignard reaction, the stereochemistry of which is well known. The NMR spectra of these epimeric alcohols are also discussed, and it is suggested that the chemical shifts of the methylene protons alpha to the ethoxycarbonyl group and of the proton of the hydroxyl group gives useful data for their stereochemical assignments. From these results, it is evident that the Reformatsky and the Grignard reactions proceed in a similar fashion; that is, the entering group predominantly approaches to the carbonyl group from the equatorial side. The stereoselectivity of the Reformatsky reaction is slightly less than that of the Grignard reaction.
  • Masayoshi Ishige, Koji Sakai, Masatoshi Kawai, Kazuo Hata
    1971 Volume 44 Issue 4 Pages 1095-1101
    Published: 1971
    Released: March 27, 2006
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    The reaction of benzyl alcohol has been examined over stabilized nickel (S-Ni) catalysts which have been modified by treating the catalyst surface with solutions of sodium compounds; this has been done in order to obtain some information about the relation between the behavior of the molecule adsorbed on the metal catalyst and the chemical nature of the catalyst surface. On the basis of the fH, fCH3, and fCHO values, which were defined as representing the catalytic activity for the formation of benzene, toluene, and benzaldehyde respectively, the variation in the activity for each modified S-Ni was evaluated. The general aspects may be summarized as follows: (1) The reaction is generally retarded with an increase in the amount of a sodium compound which is adsorbed on the catalyst during the modification process. (2) When the modification is of a lower grade, the effect of additives on the catalytic activity represented by f values is in the following order: NaNO3<NaOH<Na2S2O3<NaI<NaBr<NaCl. (3) A proper amount of NaCl on the catalyst promotes the reaction. The increase in SH and SCH3 values, which were defined as representing the selectivity factors for the formation of benzene and toluene toward that of benzaldehyde, is roughly associated with the increase in the corresponding f values.
  • Shizunobu Hashimoto, Koji Kano, Kazuo Ueda
    1971 Volume 44 Issue 4 Pages 1102-1106
    Published: 1971
    Released: March 27, 2006
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    The photochemical reduction of 4-nitropyridine has been investigated in hydrochloric acid-isopropyl alcohol solutions. 4-Nitropyridine was not photoreduced in isopropyl alcohol, whereas when the photolysis was carried out in hydrochloric acid-isopropyl alcohol solutions, the photoreduction of 4-nitropyridine proceeded from its n* triplet state to give 4-hydroxylaminopyridine in a quantitative yield. The quantum yields for the disappearance of 4-nitropyridine in hydrochloric acid-isopropyl alcohol solutions increased with the concentration of hydrochloric acid up to 3.6×10−2 mol l−1 (Φ=0.27–0.94). These results suggest that the hydrogen abstraction of photoexcited 4-nitropyridine proceeds electrophilically because of the decrease in the electron density of the nitro group, in decrease resulting from the protonation of heterocyclic nitrogen and the n* excitation of the nitro group.
  • Ichiro Kijima, Keisuke Okuda, Yoshimoto Abe
    1971 Volume 44 Issue 4 Pages 1106-1107
    Published: 1971
    Released: March 27, 2006
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    Trimethylsiloxytri-t-butoxysilane (I), bis(trimethylsiloxy)di-t-butoxysilane (II), and bis(trimethylsiloxy)bis(tri-t-butoxysiloxy)silane (III) were prepared by the reaction of trimethylchlorosilane with tri-t-butoxysilanol, di-t-butoxysilanediol, and bis(tri-t-butoxysiloxy)silanediol respectively. Bis(tri-t-butoxysiloxy)dimethylsilane (IV) was also obtained by the reaction of dimethyldichlorosilane with tri-t-butoxysilanol. The reaction of dimethyldichlorosilane with di-t-butoxysilanediol or bis(tri-t-butoxysiloxy)silanediol gave tetramethyltetra-t-butoxy (V) or tetramethyltetra(tri-t-butoxysiloxy)cyclooctasiloxane (VI). These compounds were identified by means of elemental analysis, molecular-weight determination, and a study of the IR and NMR spectra.
  • Masaaki Ueki, Hiroshi Maruyama, Teruaki Mukaiyama
    1971 Volume 44 Issue 4 Pages 1108-1111
    Published: 1971
    Released: March 27, 2006
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    Sulfenamides were found to react readily with soft nucleophiles in the presence of active hydrogen compounds. A new method for the synthesis of carboxamide from metal carboxylate, sulfenamide and tertiary phosphine was developed. The effects of metal component were examined. Copper(II) salts gave the best result. In a similar way, peptides were synthesized by the reaction of copper(II) salts of acylamino acid, or free acylamino acid in the presence of cupric chloride and triethylamine, with NPS-amino acid derivatives and triphenylphosphine. When organo-mercuric compounds such as dianisylmercury were used in place of cupric chloride and triethylamine in the above reaction, almost complete retention of configuration was observed by the Young test.
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