Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 49 , Issue 10
Showing 1-50 articles out of 52 articles from the selected issue
  • Michio Mashima, Takao Takase, Shinroku Fukuda, Norio Baba
    1976 Volume 49 Issue 10 Pages 2653-2657
    Published: 1976
    Released: April 19, 2006
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    The solvation numbers of LiCl and LiI, and of KI for comparison, in water–MeOH mixtures and water–i-PrOH mixtures were determined at an infinite dilution at 25 °C from the adiabatic compressibility. The heats of solution of these salts were also determined. In general, with an increase in the concentration of alcohol the solvation number increases initially to reach a maximum at 10–30 mol% alcohol, then it decreases to a minimum and increases again from about 75 mol% alcohol. The maximum solvation numbers of the salts determined are as follows: LiCl 11.2 mol/mol at 30 mol% MeOH; LiCl 11.5 mol/mol at 15 mol% i-PrOH; LiI 8.2 mol/mol at 12 mol% i-PrOH and KI 14.0 mol/mol at 10 mol% i-PrOH. The larger the cation, the larger the solvation number. Also, the composition of the solvant where the salt containing larger ions has a maximum solvation number has a lower concentration of alcohol. The maximum solvation number of LiI containing a larger anion is smaller than that of LiCl because an iodide ion has a much larger structure-breaking effect than a chloride ion. By the way, there seems to be difference in the structure of the mixed solvent before and after the maximum solvation number.
  • Kazuko Sasaki Kunihisa, Seiichi Hagiwara
    1976 Volume 49 Issue 10 Pages 2658-2663
    Published: 1976
    Released: April 19, 2006
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    The phase transitions of cholesteryl nonanoate were studied by means of a newly constructed apparatus for thermal analytic microscopy incorporating a thermoelement. It was possible to determine the heat of mesophase transitions more accurately. The transition values of cholesteryl nonanoate on cooling were obtained with the same accuracy as those on heating. The heat of the smectic-solid transition was obtained by slow cooling, which suppressed the supercooling. The vortices caused by cholesteric spherulites, which are similar to those of cholesteryl octanoate, change to circular arrangements of batonnets in the smectic phase. Color changes were observed at the cholesteric-smectic transition in extremely thick specimens. The relations between texture, color, and heat at the cholesteric-smectic transition of cholesteryl nonanoate are discussed.
  • Tohr Yamanaka
    1976 Volume 49 Issue 10 Pages 2664-2668
    Published: 1976
    Released: April 19, 2006
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    A method of estimating the acid-base property of the active sites in terms of the correlation between the catalytic activities of various solids and their H0,max values is presented. The H0,max denotes an H0 value of the strongest acidic sites and/or conjugate acids of the strongest basic sites. The types of catalytic actions over oxides, hydroxides, a sulfide, sulfates, phosphates, tungstates, and multi-component solid acids in the liquid-phase isopropylation of m-cresol without a solvent were classified into three groups: via a carbonium ion, via a carbanion, and concerted actions. The selectivity for the ortho-isopropylation over every catalyst increased with the increase of H0,max, and this effect of H0,max was explained by the orientation of the adsorbed m-cresol on the catalyst surface.
  • Tohr Yamanaka
    1976 Volume 49 Issue 10 Pages 2669-2673
    Published: 1976
    Released: April 19, 2006
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    γ-Al2O3 was impregnated with various metal sulfates, calcined, and used as catalysts in the liquid-phase isopropylation of m-cresol at 250–300 °C, with the propylene pressure in the range from 15 to 79 kg/cm2. The catalytic activities of the sulfates were in the order: Al2(SO4)3>ZnSO4≈NiSO4>FeSO4>CuSO4>Li2SO4≈ none≈CaSO4>Na2SO4. The order of the selectivity Φ for ortho-isopropylation over para-isopropylation was opposite to that of the catalytic activity. FeSO4/Al2O3 catalysts resulted in the best Φ value and fairly high activity, which were independent of the calcination temperature over the range of 300–500 °C. The formation of Brønsted acidic sites with 1≤H0≤3 as catalytically-active sites was estimated for the FeSO4/Al2O3 and ZnSO4/Al2O3 catalysts.
  • Eiji Kubota, Masatoki Yokoi
    1976 Volume 49 Issue 10 Pages 2674-2678
    Published: 1976
    Released: April 19, 2006
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    The conductance of tris(1,10-phenanthroline)iron(II) sulfate, Fe(phen)3SO4, and chloride, Fe(phen)3Cl2, has been measured in water-methanol mixed solvent at 25 °C. The data of the sulfate could be explained by means of the Fuoss-Onsager equation (1957) and the Fuoss-Onsager-Skinner equation (1965) on the assumption that the salt is completely dissociated in the entire composition range of the solvent system. Application of the Fuoss-Hsia equation which contains a c3⁄2 term gave association constants increasing from a value of KA=40 in water to KA=3900 in methanol. The logKA vs. 1/D plot is in good agreement with ion association theoreies. The limiting equivalent conductance of Fe(phen)32+ ion was estimated to be 34.3 in water and 62.3 in methanol.
  • Michio Kondo
    1976 Volume 49 Issue 10 Pages 2679-2682
    Published: 1976
    Released: April 19, 2006
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    Dual fluorescence from N-methylsalicylamide (1) in alcoholic solutions was observed under excitation by 280 nm light, and was ascribed to two different molecular species: one with and the other without intramolecular proton transfer in the lowest excited singlet state. Some related compounds having two identical chromophores showed similar dual emission spectra with weak emission bands at shorter wavelengths. This fact was explained as being due to the intramolecular energy transfer between the two chromophores in the excited state. From the temperature dependence of the intensity ratio of the two emission bands for these compounds, the difference between the activation energies for the two emissive states was estimated.
  • Keizo Ogino, Yukinori Ichikawa
    1976 Volume 49 Issue 10 Pages 2683-2686
    Published: 1976
    Released: April 19, 2006
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    The solubilities of sodium soaps of odd carbon-number fatty acids were measured at various temperatures and the Kraft points of the soaps were determined from the phase diagrams showing the temperature dependence of equilibria among monomers, micelles, and hydrated solid. It was found that the Kraft points were related with the carbon numbers of the fatty acids in a zig-zag curve.
  • Totaro Imasaka, Teiichiro Ogawa, Nobuhiko Ishibashi
    1976 Volume 49 Issue 10 Pages 2687-2695
    Published: 1976
    Released: April 19, 2006
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    The lasing and spectroscopic properties of coordination compounds of Calcein Blue with aluminium, calcium, strontium, and barium in water and in a water–ethanol mixture were investigated. The chelate formation improved the lasing properties of Calcein Blue, since the fluorescence quantum yield was increased by the formation of rigid rings in the molecule, and the lasing wavelength could be modified by the metal ion. By using these coordination compounds, tunable laser emissions were observed in the spectral range of 400–478 nm with a low threshold excitation intensity. The threshold excitation intensities excited by the nitrogen laser, the pulse width of which was very short (2.5 ns), were formulated by means of the spectral parameters for such molecules as its Stokes shift was large and its singlet-singlet absorption could be ignored. The calculated values obtained by this formula agreed well with the experimental values in water.
  • Michio Kimura, Toshiyuki Hirohashi, Hisao Yamamoto
    1976 Volume 49 Issue 10 Pages 2696-2700
    Published: 1976
    Released: April 19, 2006
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    The crystal structure of the title compound (SL-573), crystallized from an ethyl acetate solution, has been determined by the single-crystal X-ray diffraction method. The crystals are monoclinic, with the space group P21/a, and these cell constants: a=17.395(11), b=8.371(5), c=10.871(7) Å, β=99°56(4)′, and Z=4. The intensities were measured visually from equi-inclination integrated Weissenberg photographs taken with Cu Kα radiation. The structure was solved by the symbolic addition method. The final R factor was 0.119 for 3284 reflections. The molecules are placed in pairs around the centers of symmetry and are linked by van der Waals’ distances less than 3.94 Å. The dihedral angle between the quinazoline and phenyl ring planes was found to be 42.8°.
  • Koichi Kobayashi, Nobuhiro Watabe, Tsunetaka Sasaki
    1976 Volume 49 Issue 10 Pages 2701-2705
    Published: 1976
    Released: April 19, 2006
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    The removal of an anionic dye, Scarlet Red, a zwitterionic dye, Congo Red, and a cationic dye, Crystal Violet, from aqueous solutions was studied by the method of adsorbing particle flotation, using bentonite and benzylhexadecyldimethylammonium chloride as flotation agents. More than 99% of the Crystal Violet and Scarlet Red and 96% of the Congo Red could be floated under optimum conditions. It was found that a larger amount of a cationic surfactant was required for the flotation with an increase in the anionic nature of the dye ions, although the flotation was efficient irrespective of the ionic nature of dyes used. From this fact, the flotations of anionic and cationic dyes were confirmed to differ from each other in that the cationic-dye ions are floated by a direct exchange adsorption on bentonite, while the anionic-dye ions are floated by the adsorption on bentonite through the bimolecular layer of the cationic surfactant. The flotation efficiency of a dye ion, particularly of zwitterionic dye, was confirmed to depend on the pH.
  • Yoshihumi Kusumoto, Yasuhiko Gondo, Yoshiya Kanda
    1976 Volume 49 Issue 10 Pages 2706-2712
    Published: 1976
    Released: April 19, 2006
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    The delayed fluorescence observed in the mixed crystals of benzo[f]quinoline in biphenyl host has been found to be independent of temperature in the low temperature region from 90 K down to liquid helium temperature, and subtraction of this temperature-independent contribution from the observed total delayed fluorescence intensity above 90 K has given straight-line fits of the logIDFIP2 vs. 1/T plots, that is, a single activation energy has been obtained over the whole temperature range studied, instead of two different ones as usually assumed. Such a correction has also been given to a new attempt of logIDF vs. 1/T plots successfully. Moreover, the decay behavior of the delayed luminescence has been studied over the wide temperature and concentration range. It has been concluded that the decay behavior of the temperature-independent delayed fluorescence may mainly be responsible for the nonexponential decay of the delayed fluorescence around 77 K.
  • Yoshio Matsunaga, Tomio Tanaka
    1976 Volume 49 Issue 10 Pages 2713-2718
    Published: 1976
    Released: April 19, 2006
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    Complex TCNQ, anion radical salts containing quinolinium, isoquinolinium, and their methyl derivatives were prepared. Quinolinium and cations having molecular envelopes of 2-methylnaphthalene form 1 : 2 salts, whereas isoquinolinium and cations having molecular envelopes of 1-methylnaphthalene give 2 : 3 salts. Only N-methylquinolinium forms salts containing the solvent of crystallization. The room temperature resistivities of the polycrystalline compactions are in the range from 0.5 to 3.9 ohm cm, and the Seebeck coefficients are in the range from −41 to −54 μV/deg for the 1 : 2 salts and in the range from −12 to −23 μV/deg for the 2 : 3 salts. The diffuse reflection spectra of all the salts are similar to each other. A splitting of the band in the 10×103 cm−1 region was observed only for the 1 : 2 salts. In the total reflectance spectra, the salts show Drude-like edges in the region from 6×103 to 8×103 cm−1.
  • Kenji Iwasaki, Masami Tanaka, Tsunetake Fujiyama
    1976 Volume 49 Issue 10 Pages 2719-2723
    Published: 1976
    Released: April 19, 2006
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    Light-scattering spectra were observed for binary solutions of carbon disulfide–chloroform at various concentrations. The relation between the Rayleigh-line intensity and the concentration fluctuation was derived. Using the proposed relation and the observed Rayleigh intensity, the concentration dependence of the concentration fluctuation was then determined. The results suggest that chloroform and carbon disulfide molecules have a tendency to get together in the binary solution.
  • Jun Koike, Tetsuo Suzuki, Tsunetake Fujiyama
    1976 Volume 49 Issue 10 Pages 2724-2730
    Published: 1976
    Released: April 19, 2006
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    Raman intensities were observed at various concentrations. The observed lines were: the ν8 line of CH3CN (in CCl4 and CH3I), the ν3 line of CH3I (in CCl4), and the ν2 line of CHCl3 (in CCl4). Even after the elimination of the local-field effect, the Raman intensities showed concentration dependencies. The observed solvent effects were explained quantitatively by the use of the dipole interaction model. The polarizability and hyperpolarizability derivatives were determined for the ν8 fundamental of CH3CN. The criteria for the internal standard method were discussed quantitatively.
  • Keishiro Shirahama
    1976 Volume 49 Issue 10 Pages 2731-2734
    Published: 1976
    Released: April 19, 2006
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    The effect of added electrolyte on micelle-catalyzed reaction was analyzed. The log [L.S] vs. log (total counter ion concentration) plot gives a straight line, where [L.S] is a limiting slope on a rate-surfactant concentration plot at an infinitely dilute micellar concentration. The slope is related to the number and the magnitude of the Coulombic term that may be included in the concentration effect of reactants, and in the intrinsic micellar effect, or the relative stabilization of a transition state in the presence of micelles. The above treatment was applied to (1) the hydrolysis of trimethyl orthobenzoate in sodium dodecyl sulfate solution, (2) the fading reaction of Crystal Violet in hexadecyltrimethylammonium bromide (CTABr) solution, and (3) the nucleophilic substitution reaction of 2,4-dinitrofluorobenzene in CTABr solution. It was found that the concentration effect is predominant in (1), while the relative stabilization of the transition state occurs in (2) and (3) in addition to the concentration effect.
  • Noriko Iwasaki
    1976 Volume 49 Issue 10 Pages 2735-2738
    Published: 1976
    Released: April 19, 2006
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    Force constants K(Hg–C) were evaluated for a series of methylmercury compounds: CH3HgX (X=CH3, F, Cl, Br, I, CN, SCN, As(CH3)3, SCH3, SHgCH3, and S(HgCH3)2). It was found that K(Hg–C) increases in the following order of X: S(HgCH3)2(1.86)<I(2.27)<SCH3(2.33)=CH3(2.330)<As(CH3)3(2.37)≤Br(2.377)≤SHgCH3(2.38)≤Cl(2.382)<SCN(2.39)<F(2.55)<CN(2.61 md/Å). This order coincides, except for the cases of CN and As(CH3)3, with the order of increase in the first ionization potential of X for X=I, SCH3, CH3, Br, Cl, and F. Since this effect of X upon K(Hg–C) is regarded as a vibrational trans influence, this order was compared with that of the coupling constants in NMR, J(199Hg–13C) and J(199Hg–1H), and with the order of the bond-dissociation energy of CH3HgX into ·CH3 and ·HgX.
  • Kan Kanamori, Tokiko Sudani, Kiyoyasu Kawai
    1976 Volume 49 Issue 10 Pages 2739-2742
    Published: 1976
    Released: April 19, 2006
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    cis(S)-fac- and trans(S)-fac-Isomers of bis(thiodiacetato)cobaltate(III), trans(O)-mer-, s-cis(O)-fac- and u-cis(O)-fac-isomers of (thiodiacetato)(diethylenetriamine)cobalt(III) and trans(O)-mer-isomer of (3,3′-thiodipropionato)(diethylenetriamine)cobalt(III) were prepared. Their geometrical configurations were assigned on the basis of their absorption and PMR spectra. The stereochemistry of the Co(III) complex with a tridentate ligand thiodiacetate is similar to that of the Co(III) complex with iminodiacetate.
  • Hiroshi Ogino, Keiichi Tsukahara, Nobuyuki Tanaka
    1976 Volume 49 Issue 10 Pages 2743-2747
    Published: 1976
    Released: April 19, 2006
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    A kinetic study of the chromium(II) reduction of (O-bonded amino acid)pentaamminecobalt(III) complexes has been carried out in acid solutions. The second-order rate constants in M−1 s−1 (1 M=1 mol dm−3) at 25 °C and I=1.0 M (NaClO4) for α-alanine, phenylalanine, α-aminoisobutyric acid, β-alanine, β-aminobutyric acid, γ-aminobutyric acid, and ε-aminohexanoic acid complexes are 1.8×10−2, 1.5×10−2, 2.4×10−3, 7.5×10−2, 5.0×10−2, 1.22×10−1, and 1.49×10−1 respectively. The values of ΔH\ eweq lie in the range of 6.4–7.7 kcal mol−1 (1 cal=4.184 J), and those of ΔS\ eweq, in the range of −42–−37 cal K−1 mol−1, except for the α-aminoisobutyric acid complex, the ΔH\ eweq and ΔS\ eweq values of which are 11.4 kcal mol−1 and −32 cal K−1 mol−1 respectively. The role of the amino acid ligands in the inner-sphere electron-transfer reactions is discussed.
  • Katsuki Kitahama, Ryôiti Kiriyama
    1976 Volume 49 Issue 10 Pages 2748-2754
    Published: 1976
    Released: April 19, 2006
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    A new barium ferrite, Ba4Fe9O20H6, has been synthesized by a hydrothermal technique. This crystallizes in a monoclinic system with a=10.263(5), b=5.986(3), c=14.559(6) Å, β=95.20(3)°, Z=2, space group C2/m. The structure was determined by Patterson and Fourier methods from three-dimensional X-ray counter data and refined by block-diagonal least-squares calculations to R=0.098 for 1128 reflections. The structure consists of condensed layers of ferrite anions, Fe(OH)63− clusters, and Ba2+ cations; it has the character of a crystal growth from aqueous solutions. The presence of Fe2+ was confirmed; such ions are located in the condensed ferrite layer. Consequently, the true formula should be written as Ba4[FeIII(OH)6][FeIIFe7IIIO14]. This crystal is ferrimagnetic below the Nèel point of 515 K. The magnetic moment was estimated to be about 10 μB per formula unit at 0 K.
  • Takeshi Tominaga, Takuhiko Sakai, Tomohiko Kimura
    1976 Volume 49 Issue 10 Pages 2755-2758
    Published: 1976
    Released: April 19, 2006
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    The Mössbauer spectra of graphite–FeCl3 and graphite–FeCl3–AlCl3 compounds with varying FeCl3/AlCl3ratios were measured. At 298 K, the isomer shift of the Fe3+ peak of FeCl3 intercalated in the graphite–FeCl3 compounds was larger than that of pure anhydrous FeCl3, and two sets of Fe2+ quadrupole doublets appeared in the spectra of the graphite–FeCl3–AlCl3 compounds with FeCl3/AlCl3 ratios of approximately one or less. These results may be accounted for in terms of the transfer of graphite π-electrons to intercalated FeCl3.
  • Tateaki Ogata, Tadashi Fujisawa, Nobuyuki Tanaka, Hiroshi Yokoi
    1976 Volume 49 Issue 10 Pages 2759-2761
    Published: 1976
    Released: April 19, 2006
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    Solvent effects on the ESR spectra of bis(2,6-dimethyl-3,5-heptanedionato)copper(II) ([Cu(dibm)2]) and a similar copper(II) complex were investigated in some detail. A clear relationship between the ESR parameters and the donicity of the solvents was confirmed, and this is discussed with the intention of investigating the donicities of water and methanol. The donor number for water in an aqueous solution was estimated to be about 30 from a precise analysis of the ESR spectra of [Cu(dibm)2] in water–methanol mixtures.
  • Sakae Uemura, Akio Toshimitsu, Masaya Okano
    1976 Volume 49 Issue 10 Pages 2762-2764
    Published: 1976
    Released: April 19, 2006
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    A simple synthesis is given for the stable monoalkylthallium(III) dichloride, C6H5CH(OR)CH2TlCl2 (1) from the corresponding diacetate (2) and potassium chloride in methanol or acetonitrile. 1(R=Me) reacts slowly with potassium and copper (I) halides to give mainly α-methoxystyrene and C6H5CH(OMe)CH2X (X=Cl, Br, I), respectively. It is concluded that 1(R=Me) is less susceptible than 2(R=Me) to SN1, SN2, and SNi reactions.
  • Meguru Tezuka, Osamu Sekiguchi, Yasukazu Ohkatsu, Tetuo Osa
    1976 Volume 49 Issue 10 Pages 2765-2769
    Published: 1976
    Released: April 19, 2006
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    Cobalt(II) tetraphenylporphyrins catalyzed the autoxidation of acetaldehyde giving peracetic acid quantitatively. The p-substituents of phenyl groups of tetraphenylporphyrin influenced the catalytic activity, cobalt(II) tetra(p-methylphenyl)porphyrin being remarkably active. The effect of the base added into the reaction system was such that an appropriate quantity of the base gave rise to a maximum rate of oxidation. The rate equation was determined experimentally. From the results of kinetics and ESR study, it was concluded that an oxygen molecule activated through the electron transfer from a cobalt(II) ion abstracted the hydrogen of acetaldehyde to initiate the autoxidation.
  • Yoshiyuki Takahashi, Soichi Otsuka, Hideyuki Masuda, Minoru Hirota, Yo ...
    1976 Volume 49 Issue 10 Pages 2770-2774
    Published: 1976
    Released: April 19, 2006
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    2-(N-Methylanilino) and 1-methyl-2-phenylimino derivatives of pyridine and quinoline were prepared as models for the amino and the imino tautomers of 2-anilino-pyridine and -quinoline. The ultraviolet, infrared and NMR spectra of these compounds were compared with those of the model compounds. The spectral data show that the amino tautomers are by far preferred in various solvents. The pKa measurement on 1-methyl-2-phenylimino-1,2-dihydropyridine allows the assumption of the tautomeric equilibrium constant.
  • Ichiro Hirao, Taketoshi Kito, Takatomo Funamoto, Taketoshi Murakami, K ...
    1976 Volume 49 Issue 10 Pages 2775-2779
    Published: 1976
    Released: April 19, 2006
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    O-Carboxylation of the alcohol (ROH) occurred to give alkali alkyl carbonate in a good yield when carbon dioxide was introduced into the mixture of an alkali salt of a weak acid, alcohol, and acetone (or THF) at room temperature under atmospheric pressure. Such alkali salts as PhOM, p-R′C6H4OM (R′=CH3, CH3O, or Br), Et2NCSSM, NaCN, and C6H4(CO)2NK (M=K or Na) were effective. The mixture of HOC6H4COOM and ROCOOM was obtained from the reaction using MOC6H4COOM as an alkali salt. However, the mixture was composed of equimolar amounts of p-HOC6H4COOM and ROCOOM when p-MOC6H4COOM was used. In this reaction, two mechanisms have been examined.
  • Norio Kobayashi, Tamotsu Fujisawa
    1976 Volume 49 Issue 10 Pages 2780-2783
    Published: 1976
    Released: April 19, 2006
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    Sodium diethyldithiocarbamate (1) and tetraethylthiuram disulfide (2) have been found to react with excess mercury(II) chloride (HgCl2) in water to give complexes with the general formula Et2NCS2HgS2CNEt2·(HgCl2)m−1, where the m value can be as high as five. The complex with m=2 was isolated and characterized. The reaction pathway was discussed in some detail. Also studied were the reactions of 2 with HgCl2 in organic solvents.
  • Tatsuo Takahashi, Takefumi Koiso
    1976 Volume 49 Issue 10 Pages 2784-2789
    Published: 1976
    Released: April 19, 2006
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    The thermodynamic ion-association constants of hexaamminechromium(III) and tris(ethylenediamine)chromium(III) with several univalent anions were determined in aqueous solutions at 25.0 °C. The logKcon values obtained by the conductometric method are 1.37 for [Cr(NH3)6]3+–Cl, 1.58 for [Cr(en)3]3+-Cl, 1.57 for [Cr(NH3)6]3+–Br, 1.50 for [Cr(en)3]3+–Br, 1.53 for [Cr(NH3)6]3+–NO3, and 1.49 for [Cr(en)3]3+–NO3. The log KSP values obtained by the spectrophotometric method are 1.65 for [Cr(en)3]3+–Cl, 1.46 for [Cr(en)3]3+–Br, and 0.90 for [Cr(en)3]3+–ClO4; the value for [Cr(en)3]3+–ClO4 could be indirectly calculated from the apparent ion-association constant of [Cr(en)3]3+–Br determined in the solutions containing both bromide and perchlorate ions. Though the detailed comparison of the ion-association constants obtained in this study was limited, it could be concluded that the Kcon values were in relatively good agreement with the Ksp values obtained on the given ion-pairs and that the ion-association constants of chromium(III) complex cations with several univalent anions are slightly less than those of the corresponding cobalt(III) complex cations with their anions.
  • Akio Takuwa
    1976 Volume 49 Issue 10 Pages 2790-2799
    Published: 1976
    Released: April 19, 2006
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    3-Acyl-1,2-naphthalenediols and 1,2-naphthalenediol monoacyl esters were obtained from the photochemical reactions of 1,2-naphthoquinones with aliphatic aldehydes. 3-Halogeno-1,2-naphthoquinones gave the corresponding 1,2-naphthalenediol monoacyl esters, 3-acyl-1,2-naphthalenediols, which are the same products as those from the photochemical reactions of 1,2-naphthoquinone with those aldehydes and 3-halogeno-4-acyl-1,2-naphtoquinone when they were irradiated in aldehydes. 3-Methyl-1,2-naphthoquinone, however, gave the corresponding 1,2-naphthalenediol monoacetate and 3-methyl-4-acetyl- 1,2-naphthoquinone when it was irradiated in acetaldehyde. These photochemical reactions were applicable for syntheses of 3-acyl-1,2-naphthalenediols and 1,2-naphthalenediol monoacyl esters.
  • Hiroshi Sakurai, Akira Tatematsu, Hisao Nakata
    1976 Volume 49 Issue 10 Pages 2800-2801
    Published: 1976
    Released: April 19, 2006
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    The 2E doubly charged ion mass spectra of twelve simple monosubstituted aromatic compounds were recorded. The spectral pattern of these compounds can be classified into three types. When the substituent is strongly electron-donating such as the amino or dimethylamino group, a very intense molecular ion peak appears, no fragment ion peak being observed. Phenol, anisole, toluene, and chlorobenzene show both molecular and fragment ion peaks in varying intensities. The parent benzene itself behaves similarly. Only fragment ion peaks were observed for nitrobenzene and aromatic carbonyl compounds such as benzaldehyde, acetophenone, methyl benzoate, or benzoic acid. The major fragmentation reactions are discussed.
  • Hisao Imai
    1976 Volume 49 Issue 10 Pages 2802-2804
    Published: 1976
    Released: April 19, 2006
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    The dehydration of diethyl ether was studied on synthetic nickel oxide–silica–alumina catalysts in the temperature range of 340–400 °C and at pressures less than 50 Torr. It was found that ethylene, butenes, water, and small amounts of carbon monoxide and methane were formed on the catalysts of lower nickel content. The rate constant for the formation of butenes showd a maximum on the catalyst of 10 atom% nickel. The mechanism of the formation of the butenes was discussed by studying the catalytic dehydration of various ethers.
  • Kazutoshi Yamada, Kiyoshi Katsuura, Hideaki Kasimura, Hirotada Iida
    1976 Volume 49 Issue 10 Pages 2805-2810
    Published: 1976
    Released: April 19, 2006
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    The irradiation of the pyrazine derivative with an α-carbonyl substituent (1) under a nitrogen atmosphere gave hydroxypyrazine (2) and two solvent adducts (3 and 4). In the case of 1e, the charge-transfer complex of pyrazine and dihydropyrazine, produced by the reduction of the pyrazine, was isolated. The mechanism of this photoreaction was similar to that of flavine. The attack of oxygen on dihydropyrazine produced 2. Furthermore, the photoreduction with DTT occurred through the intermediate, which was similar to the case of flavine. The reaction rates of various pyrazines were measured. The quenching studies indicate that the photoreaction proceeds via the n-π* triplet state.
  • Masayoshi Okano, Takaaki Aratani
    1976 Volume 49 Issue 10 Pages 2811-2814
    Published: 1976
    Released: April 19, 2006
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    When acetone, ethyl methyl ketone (EMK), and cyclohexanone were heated with manganese(III) acetate dihydrate in a mixed solvent of glacial acetic acid and acetic anhydride at 100 °C, acetoxy ketones were obtained as common products. Furthermore, ketone dimers (1,4-diketones) were obtained from acetone and cyclohexanone, which also gave 1,2,3,4-tetrahydrodibenzofuran. When mixtures of these ketones and 1-hexene were heated with the oxidant, saturated and unsaturated ketones and γ-acetoxy ketones were obtained as common products, and 2-propylchromene was obtained as a new product from the cyclohexanone-1-hexene mixture. The formation courses of these reaction products are discussed.
  • Hiroko Sato, Takenori Kusumi, Kyoto Imaye, Hiroshi Kakisawa
    1976 Volume 49 Issue 10 Pages 2815-2816
    Published: 1976
    Released: April 19, 2006
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    1,3-Dipolar addition of the nitronic ester (3) to methyl acrylate afforded regiospecifically the isoxzolidine (4), which produced the oxime ether (7) on heating. Reduction of 7 followed by hydrolysis gave the hydroxy amino acid (6), which is known to improve anitibiotic activities. The nitronic ester (3) also reacted regio- and stereospecifically with methyl crotonate to produce the adduct (8). Pyrolysis of (8) followed by reduction and hydrolysis gave the erythro hydroxy amino acid (11).
  • Kaku Uehara, Yoshiyuki Ohashi, Makoto Tanaka
    1976 Volume 49 Issue 10 Pages 2817-2820
    Published: 1976
    Released: April 19, 2006
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    The bivalent metal complexes of 2,4-pentanedione(M(acac)2) catalyzes the conversion of 3-(1-hydroxy-2,2,2-trichloroethyl)-2,4-pentanedione(A) into chloral and acetylacetone(Hacac) in a chloroform solution. The order of activity of M(acac)2 as the catalyst is: Mg(II), Mn(II)>Co(II)>Ni(II)>Cu(II)<Zn(II). It was found that the catalyzed reaction proceeds through saturation-type kinetics. The Lineweaver-Burk-type plots show linear relationships and are consistent with a mechanism in which a preequilibrium complex formation between M(acac)2 and a substrate is followed by the rate-determining decomposition to give the products. Acetylacetone acts as a competitive inhibitor for the Cu(acac)2-catalyzed reaction. The third stability constant for the Cu–Hacac chelate system can be evaluated from the inhibitor constant as log K3=4.3. The retrograde aldol reactions of 3-(1-hydroxy-2,2,2-trichloroethyl)-5-methyl-2,4-hexanedione and 3-(1-hydroxy-2,2,2-trichloroethyl)-4-phenyl-2,4-butanedione were studied in the same manner as 3-(1-hydroxy-2,2,2-trichloro-ethyl)-2,4-pentanedione. A possible mechanism for the catalysis is proposed.
  • Hiroo Tanaka, Ryoichi Senju
    1976 Volume 49 Issue 10 Pages 2821-2823
    Published: 1976
    Released: April 19, 2006
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    Polyvinylamine which contained 95.6 mol% amine units was obtained when the Hofmann degradation was applied to polyacrylamide by use of a very slight excess of sodium hypochlorite and a large excess of sodium hydroxide at 0 to −15 °C for about 15 h. Polyvinylamine hydrochloride (PVAm·HCl) was isolated almost quantitatively as a white powder. PVAm·HCl was freely soluble in water, but insoluble in organic solvents such as methanol, acetone, dioxane, N,N-dimethylformamide (DMF), and dimethyl sulfoxide (DMSO). The desalting of PVAm·HCl was performed by passing its aqueous solution through columns of ion exchange resins. The product containing 30.5% nitrogen was obtained in reasonable yield. Polyvinylamine was freely soluble in water, acetic acid, or lower alcohols, but insoluble in solvents such as acetone, dioxane, DMF, and DMSO.
  • Yoshihisa Watanabe, Masakazu Yamashita, Mineo Igami, Take-aki Mitsudo, ...
    1976 Volume 49 Issue 10 Pages 2824-2827
    Published: 1976
    Released: April 19, 2006
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    The reaction of carboxylic and carbothioic esters with disodium tetracarbonylferrate has been studied. Aryl and thiolic esters reacted with the ferrate under mild conditions to give aldehydes after the reaction mixture had been quenched with acetic acid, but alkyl esters did not. 3-Benzylidenephthalide and phthalide gave 2-phenyl-1,3-indanedione and a dimeric product respectively.
  • Otohiko Tsuge, Akitaka Inaba
    1976 Volume 49 Issue 10 Pages 2828-2832
    Published: 1976
    Released: April 19, 2006
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    The reaction of enamino ketone 1, derived from acetylacetone, with benzoyl isocyanate (4) gave the isomeric benzoylcarbamoyl derivatives 6 and 9, and/or 2-pyridone 7, depending upon the reaction conditions. Similarly, enamino ketone 2, derived from benzoylacetone, reacted with 4 to afford the isomeric benzoylcarbamoyl compounds 12, 13, and/or 2-pyrone 14. It has been found that the carbamoyl compound 12 was thermally converted into 13 and 14. Enamino ketones 1 and 2 reacted with thiobenzoyl isocyanate (5) at room temperature to yield the 2-pyridones 7 and 15, respectively. On the other hand, enamino ketones 3, derived from benzoylacetaldehyde and secondary amines, reacted with 4 to give the corresponding 2-benzoylcarbamoyl-2-penten-2-one compound 18, while in the reaction with 5, 3 gave the 1,3-thiazin-4-one 19 and/or (4+2) cycloaddut 20.
  • Fukiko Yamada, Osamu Kitano, Soichi Shindo, Harunori Ueda
    1976 Volume 49 Issue 10 Pages 2833-2836
    Published: 1976
    Released: April 19, 2006
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    The reaction kinetics of 3- and 2-butenenitriles with 2-alkylimidazoles were studied by using NMR, and a mechanism consistent with the results is proposed. The imidazoles were active in isomerizing 3-butenenitrile to 2-butenenitrile, and then reacted only with the 2-butenenitrile to give the corresponding 1-(2-cyano-1-methylethyl)imidazoles. These consecutive reactions, isomerization and cyanoethylation, are second-order over all. For example, in the reaction of 3-butenenitrile with imidazole, the rate measurements of the isomerization at various temperatures, ranging from 30 to 90 °C, afforded the activation parameters of Ea=14.6 kcal/mol and ΔS\ eweq=−35.3 cal/degree. On the other hand, in the case of 2-butenenitrile with imidazole, the measurements of the cyanoethylation at 60–100 °C gave these parameters; Ea=15.3 kcal/mol and ΔS\ eweq=−45.7 cal/degree. In this case, the rates of the isomerization (k1=6.0×10−6 l/mol s at 60 °C) are approximately ten times larger than those of the cyanoethylation (k2=0.53×10−6). A mechanism is discussed on the basis of their NMR spectral and kinetic data.
  • Sinpei Kozima, Kazuhiko Kobayashi, Mituyosi Kawanisi
    1976 Volume 49 Issue 10 Pages 2837-2839
    Published: 1976
    Released: April 19, 2006
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    The photochemical reactions of dibutyltin, (Bu2Sn)m, with alkyl monohalides, R′X, give Bu2R′SnX-type compounds by the insertion of the intermediately formed dibutylstannylene to the C–X bond of alkyl halides. This provides a facile method for preparing Bu2R′SnX compounds, since the reaction proceeds quickly under mild conditions giving the products in good yields, the only by-product Bu3SnX which can be distilled being obtained only in a low yield. The reactions with dihalomethanes were also successful. The reaction pathway is discussed in connection with the reactivities of the substrates.
  • J\={u}ro Ojima, Tadayoshi Yokomachi, Akihiko Kimura
    1976 Volume 49 Issue 10 Pages 2840-2844
    Published: 1976
    Released: April 19, 2006
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    In order to establish the effect of the annelation of benzene rings on [4n+2] annulenes, the syntheses of benzannelated dehydroannulenes were attempted. Dibenzo-tetrakisdehydro[ 18]annulenes (IIa and IIb) were prepared according to the reaction sequence developed in the synthesis of tetramethyltetrakisdehydro[18]annulene (I) from o-ethynylbenzaldehyde (VIII); both of them proved to be unstable. Tribenzo-bisdehydro[14]annulene (XVII) was also prepared from VIII by a double Wittig reaction, followed by oxidative coupling. An examination of the NMR spectrum indicated that XVII is atropic.
  • B. T. Thaker, P. K. Bhattagharya
    1976 Volume 49 Issue 10 Pages 2845-2848
    Published: 1976
    Released: April 19, 2006
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    Nitration of the coordinated ligands in the complexes bis[1-(2-hydroxyphenyl)ethylideneamine or its methyl derivative]Cu(II) and N,N′-ethylene or propylene bis[1-(2-hydroxyphenyl)ethylideneaminato]Cu(II) have been carried out. Similar nitration reactions of mixed diamine Schiff base complexes of Cu(II) have also been carried out. The substitution products have been characterized by elemental analyses, comparison with authentic samples in case of binary complexes and by means of magnetic moments, electronic and IR spectral studies. The orientation of incoming substituents in the chelates is found to be the same as that in uncomplexed 2-hydroxyacetophenone or methyl substituted 2-hydroxyacetophenone. Nitration reactions in case of mixed ligand complexes confirm the structure.
  • Harumi Endo, Otohiko Nomoto
    1976 Volume 49 Issue 10 Pages 2849-2851
    Published: 1976
    Released: April 19, 2006
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    The sound velocity in water aqueous solutions increases with increasing temperature and reaches the maximum velocity (Vp) at a peak temperature (Tp). In the present paper, the concentration dependence of Tp and Vp in ammonium halides are reported. It was found empirically that the relationship between the hydration number and the slope (ΔTp⁄μ of Tp at infinite dilution for many electrolytes is linear, but that for ammonium halides this is not the case.
  • K. C. Tewari, H. N. Singh, V. S. Singh
    1976 Volume 49 Issue 10 Pages 2852-2854
    Published: 1976
    Released: April 19, 2006
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    The mechanism of the oxidation of α-hydroxy acids by ceric sulfate in sulfuric acid medium has been reexamined in the temperature range 15–30 °C and the thermodynamic parameters have been calculated. The role of HSO4 ion as an active inhibitor has been discussed quantitatively.
  • G. A. Bhat
    1976 Volume 49 Issue 10 Pages 2855-2857
    Published: 1976
    Released: April 19, 2006
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    By using the same current-time (I-t) curves, electrochemical kinetic parameters are determined by two methods, (a) using the ratio of current at a given potential to the diffusion-controlled limiting current and (b) curve fitting method, for the reduction of Cu(II)–CyDTA complex. The analysis by the method (a) shows that the rate determining step involves only one electron although the overall reduction of the complex involves two electrons suggesting thereby the stepwise reduction of the complex. The nature of I-t curves suggests the adsorption of intermediate species at the electrode surface. Under these circumstances more reliable kinetic parameters can be obtained by the method (a) compared to that of (b). Similar observations are found in the case of reduction of Cu(II)–EDTA complex.
  • Fasih A. Siddiqi, M. Nasim Beg, Abdul Haque, Surendra P. Singh
    1976 Volume 49 Issue 10 Pages 2858-2863
    Published: 1976
    Released: April 19, 2006
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    Electrolytic transport processes occurring across parchment supported membranes have been described by Nernst-Planck flux equation taking into account the membrane resistance Rm, membrane potential Em etc. Em values for various electrolytes display very interesting phenomena. In the case of 1 : 1 electrolyte the Em values are all positive, while in the case of (2 : 1) and (3 : 1) electrolytes surface charge reversal takes place. The diffusion rate sequence and selectivity of the membrane for different uni-, bi-, and tri-valent cations was found to be primarily dependent on the difference in the hydration energies of counter ions in the external solution. On the basis of Eisenman-Sherry theory the diffusion rate sequence of alkali metal cations point towards the weak field strength of the fixed charge groups. Various thermodynamic parameters, ΔH, ΔF\ eweq, and ΔS\ eweq were evaluated by applying the theory of absolute reaction rates to the diffusion process through parchment supported membranes. The values of ΔH\ eweq were found to be negative, indicating that diffusion takes place with partial immobilization in the membrane phase. The relative partial immobility was found to increase with increase in the valence of the ions constituting the electrolyte. A formal relation between ΔHhydration, ΔFhydration, and ΔShydration of cations with the corresponding values of ΔH\ eweq, ΔF\ eweq, and ΔS\ eweq for diffusion, was also found to exist for these membranes.
  • Fasih A. Siddiqi, M. Nasim Beg, Surendra P. Singh, Abdul Haque
    1976 Volume 49 Issue 10 Pages 2864-2868
    Published: 1976
    Released: April 19, 2006
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    The thermodynamic effective fixed charge density, the most important parameter governing transport phenomena in membranes, was estimated by methods of TMS, Altug and Hair and the most recent one of Kobatake based on the thermodynamics of irreversible processes. Kobatake’s equation has also been utilized for the evaluation of permselectivity of membranes. The two limiting forms of his equation for dilute and concentrated ranges gave identical values of θ (charge density) for barium phosphate membrane. The theoretical predictions for membrane potential by the equation were borne out quite satisfactorily by experimental results obtained with the investigated membranes.
  • Buta Singh, J. K. Vij
    1976 Volume 49 Issue 10 Pages 2869-2871
    Published: 1976
    Released: April 19, 2006
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    Measurements of the relative permittivity at 1 MHz and 9.27 GHz, and of the refractive index for the sodium-D line have been made for (A) o-nitrobenzaldehyde, (B) m-nitrobenzaldehyde, (C) m-chlorobenzaldehyde, and (D) p-chlorobenzaldehyde, at 15, 25, 35, and 45 °C in dilute solutions of benzene. The dielectric relaxation times τ(1) and τ(2) have been calculated using the Higasi, Koga, and Nakamura method. The results suggest that the relaxation time for the overall rotation decreases at a greater rate than the one for the internal rotation. The thermodynamic energy parameters have been calculated. The results show that the freedom of rotation of the –CHO group increases around the Calip–Carom bond as an electronegative substituent moves from the o- to m- to p- positions.
  • Rakesh Kumar Kohli, P. K. Bhattacharya
    1976 Volume 49 Issue 10 Pages 2872-2874
    Published: 1976
    Released: April 19, 2006
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    As regards the preparation and characterization of some new mixed complexes of the type MLL′ where M=Cu(II), Ni(II); L=salicylaldimine and L′=(o-hydroxybenzyl)(ethylideneamine) or o-hydroxydiphenylenethylene-amine or their derivatives, we have carried out the preparation of a few similar types of complexes where L′=2-hydroxy-1-naphthylmethyleneamine. The mixed imine Schiff’s base complexes have been prepared by treating the metal ammine complex with an equivalent amount of salicylaldehyde and 2-hydroxy-1-naphthaldehyde. Amine exchange reactions were also been carried out by treatment of mixed imine Schiff’s base complex with ethylenediamine(en) or propylenediamine(pn). The complexes of new Schiff’s base were formed where diamine have salicylaldehyde condensed at one end and 2-hydroxy-1-naphthaldehyde at the other end. The complexes have been characterized by elemental analysis, TLC analysis, conductance measurements, magnetic measurements, and spectral analysis.
  • J. Sreekantha Babu, M. M. Bokadia, K. Srinivasulu
    1976 Volume 49 Issue 10 Pages 2875-2876
    Published: 1976
    Released: April 19, 2006
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    The oscillatory phenomenon during oxidation of gallic acid with potassium bromate, catalyzed by cerium ion in acid medium with stirring was investigated. The cross section of a three dimensional graph for the regions where the oscillatory behavior can be observed is given. Effect of Ag+and Br on the oscillatory behavior was studied.
  • K. Natarajan, Umesh Agarwala
    1976 Volume 49 Issue 10 Pages 2877-2878
    Published: 1976
    Released: April 19, 2006
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    The syntheses of some new β-diketone complexes of Ru(III) with triphenylphosphine and triphenylarsine have been described. Their spectral (IR and visible) and magnetic properties have been reported. Some of them show unusual magnetic moment.
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