Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 51 , Issue 2
Showing 1-50 articles out of 84 articles from the selected issue
  • Akinori Inoue, Hiroshi Chuman, Nozomu Ebara
    1978 Volume 51 Issue 2 Pages 345-348
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The previously proposed method of studying T-T energy trasfer between like molecules using isotopic mixtures was further improved and applied to an investigation of naphthalene and phenanthrene molecules. Critical transfer distances of 15 and 13 Å were determined for naphthalene and phenanthrene, respectively. The present method has the advantage that it is free from the effect of S-S energy transfer.
  • Takayoshi Kobayashi
    1978 Volume 51 Issue 2 Pages 349-354
    Published: 1978
    Released: April 19, 2006
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    The effect of high density excitation on the phosphorescence spectra and their decay curves of crystalline uranyl(VI)nitrate hexahydrate, uranyl(VI)acetate dihydrate, and zinc uranyl(VI)acetate heptahydrate was studied using a nitrogen laser as the exciting light source. The relative emission intensity of the spectra in the shorter wavelengths decreased and the vibrational structure became broader at higher density excitations; these changes were attributed to the saturation in excitation and to the temperature increase in the irradiated volume of the sample crystal caused by the heat released in the radiationless decay process. A decrease in the decay time was also observed at high density excitations; this shortening was attributed to bimolecular quenching of triplet excitons in the crystal. The rate constant for this process in crystalline uranyl nitrate hexahydrate was measured at several temperatures between 77 and 295K; it was 2.6×10−13 cm3 s−1 at 295K for example. From this rate constant the hopping rate for a triplet exciton in crystalline uranyl nitrate hexahydrate was obtained: 4.3×108 cm3 s−1 at 295K. The activation energy for the exciton migration was found to be 320 cm−1.
  • Katsuyuki Aoyagi
    1978 Volume 51 Issue 2 Pages 355-359
    Published: 1978
    Released: April 19, 2006
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    Quasi-peaks which do not correspond to any reactant ion in the ion-molecule reaction were observed in the ion cyclotron double-resonance spectrum. The field-sweep quasi-ICDR spectrum was also observed. Expressions giving the frequencies of the quasi-peaks observed in the ion cyclotron double-resonance spectrum were obtained; the results agreed with those obtained previously. Both the ion mass and ion drift-voltage dependences of the quasi-peaks were shown. A close agreement between the calculated and measured values was obtained. A method to repress the quasi-peaks is discussed.
  • Yoshito Amako, Yoshi-ichi Sato, Akiyoshi Watanabe
    1978 Volume 51 Issue 2 Pages 360-366
    Published: 1978
    Released: April 19, 2006
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    Calculations have been performed on the energy matrix of a rigid symmetric-top molecule, HCHO, in order to determine the transition energies and intensities of the rotational sub-bands of the electronic spectrum under various magnitudes of external electrostatic fields. Though HCHO is an asymmetric-top molecule, the rotational structure of the 3390 Å band of this molecule is close to that of a perpendicular band of a symmetric-top molecule, at least, for not too small values of K. The variation in the band structures with the applied fields can be illustrated by the behavior of several selected bands, pP, pQ, rR, and rQ. Below 100 kV/cm, the overall Stark splittings have been linearly dependent on the field strength, regardless of the branch types. Over 100 kV/cm, however, a deviation from the linear dependence has been found for a certain branch. Changes in the band shape have appeared at such small values of external fields that no deviation from the linear field dependence of the overall Stark splitting has been observed. Such changes are dependent on the branch types, especially in the cases of branches with small J values and with K<J. The intensity enhancement of some forbidden bands has also been observed, the magnitude of which is proportional to the square of the field strength below 100 kV/cm. However, the relation between the intensity enhancement and the electric fields has been found to be complicated at fields over 100 kV/cm, the enhanced intensity being proportional to a coupled sum of E2 and higher terms. At a fixed electric field, a linear relation has been found between the overall Stark splitting and the various μ values assumed for the excited state. The analysis of the data has enabled us to determine the electric dipole moment of the lowest n→π* excited state of HCHO as 1.65 D.
  • Kiyoshi Otsuka, Masaki Fukaya, Akira Morikawa
    1978 Volume 51 Issue 2 Pages 367-371
    Published: 1978
    Released: April 19, 2006
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    The cis-trans isomerization of cis-2-butene caused by electronically-excited sulfur dioxide has been studied at the gas-solid interface of porous Vycor glass. All of the quantum yields for the isomerization obtained gave values larger than ≈30. Infrared studies show that the product on the glass is the polysulfone formed through the copolymerization of sulfur dioxide and cis-2-butene. These results and the kinetic data for the isomerization can be explained satisfactorily by the proposed mechanism in which the isomerization occurs through the addition and elimination of 2-butene molecules at the terminal of the polysulfone formed on the glass; the copolymerization is initiated by an electronically-excited SO2 (3B1) state.
  • Kenjiro Kondo, Masuo Yagi
    1978 Volume 51 Issue 2 Pages 372-378
    Published: 1978
    Released: April 19, 2006
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    The reaction of isomeric transition-activated 80Br was studied in the gaseous H80mBr–CH4(HBr/CH4=0.1±0.01) system. CH380Br, CH280BrBr and CH80BrBr2 were identified as the products, and their absolute yields were 1.60, 2.65, and 0.05%, respectively. The effects of Kr and Xe additives show that these products were produced only through kinetic-energy independent (thermal ionic) processes. The results are compared with those obtained in the 80mBrBr (or 82mBrBr)–CH4 system, in which the C–*Br formation proceeds mainly via kinetic-energy dependent processes, and the difference between them is explained on the basis of the cross sections for charge neutralization and capture collision complex formation of bromine ions as a function of the kinetic energies initially acquired by the 80Br and 82Br atoms. The persistent complex ion, CH480Br+, is considered to be a precursor of the product formations, and the formation of individual products is discussed on the basis of ion-molecule reactions of CH480Br+ with surrounding molecules. Furthermore, the effect of HCl and CH2=CH2 additives on the yield distribution were examined to elucidate the reaction mechanisms of the product formations.
  • Yoshiharu Usui, Michio Tsukada, Hiroko Nakamura
    1978 Volume 51 Issue 2 Pages 379-384
    Published: 1978
    Released: April 19, 2006
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    Singlet oxygen produced by the dye-sensitized reaction in an aqueous solution penetrates into the interior of the surfactant micelles of sodium dodecyl sulfate (SDS) and dodecyltrimethylammonium chloride (DTAC), reacting with the solubilized acceptors such as 9,10-dimethylanthracene, 2,5-diphenyloxazole, and 1,3-diphenylisobenzofuran. From the acceptor concentration effect on the photooxygenation quantum yield, the reactivity index (β), the ratio of the rate constant of the spontaneous decay of singlet oxygen to that of the reaction with an acceptor, is obtained in the aqueous micellar solution. It has been shown that the lifetime of singlet oxygen is mainly dependent on the solvent composition in the bulk phase from the kinetic analysis of the mixed solvent effect on the quantum yield in SDS and DTAC micellear solutions and that in a homogeneous solution.
  • Masaharu Okazaki, Keiji Kuwata
    1978 Volume 51 Issue 2 Pages 385-389
    Published: 1978
    Released: April 19, 2006
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    The ENDOR spectra of the ion-pair system of the 2,5-di-t-butyl-p-benzoquinone anion and the alkali metal cation in 1,2-dimethoxyethane were observed. The influence of the intramolecular cation migration on both the linewidth and the intensity of the ENDOR spectra was experimentally examined. The results obtained were discussed theoretically using the Kaplan-Alexander formula. The intramolecular exchange due to the cation migration was shown to be effective in ENDOR.
  • Toschitake Iwamoto, Mamoru Kiyoki, Niro Matsuura
    1978 Volume 51 Issue 2 Pages 390-393
    Published: 1978
    Released: April 19, 2006
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    Cyclohexadienyl radicals produced by γ-ray irradiation are thermally stable up to 423 K in the mother benzene clathrates Cd(en)Hg(CN)4·2C6H6, Cd(en)Cd(CN)4·2C6H6, Cd(tn)Hg(CN)4·2C6H6, and Cd(NH3)2Hg(CN)4· 2C6H6. However, no thermally stable C6H7· radicals have been observed in Cd(NH3)2Ni(CN)4· 2C6H6 and Cd(en)Ni(CN)4·2C6H6 even immediately after irradiation. The ESR spectra of C6H7· show the hyperfine splitting constants of the methylene, para, ortho, and meta protons 48, 13, 9, and 3 G, respectively.
  • Teiichiro Ogawa, Nobuaki Miyamoto, Nobuhiko Ishibashi
    1978 Volume 51 Issue 2 Pages 394-397
    Published: 1978
    Released: April 19, 2006
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    Naphthalene, 1-methylnaphthalene, 2-methylnaphthalene, 1-naphthol, 1-naphthylamine, 2-chloronaphthalene, 1-bromonaphthalene, 2-bromonaphthalene, and tetralin were excited in a very low pressure by controlled electron beam of 150–400 eV. The molecules, except those with a halogen atom, revealed an intense emission band similar to fluorescence. The band was assigned to the transition from their lowest-excited singlet state to their ground state. It was concluded that the most important process of photoemission is the excitation into a higher excited state in the primary collision and the subsequent non-radiative transfer to the lowest-excited state. The molecules showed photoemission of such excited fragments as H, CH, C2, C4H2+, CN, NH, OH, CO, CO+, HCL+, and HBr+. A two-electron process by way of an intermediate was found to be important for the formation of such fragments as CN from naphthylamine.
  • Yu-ichi Takeda, Tsuneo Matsuda, Toshio Tanaka
    1978 Volume 51 Issue 2 Pages 398-400
    Published: 1978
    Released: April 19, 2006
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    Activation parameters for rotation around the isopropyl-nitrogen bond of the title compounds were determined by the line shape analysis of 1H NMR spectra. The Ea values lie in the ranges of 58–60 kJ/mol for X=S and 52–54 kJ/mol for X=Se. The activation parameters are little influenced by the ring size of the 1,3-diheteracycloalkane moiety and the counter anions.
  • Izumi Maki, Kazuo Kitaura, Kichisuke Nishimoto
    1978 Volume 51 Issue 2 Pages 401-406
    Published: 1978
    Released: April 19, 2006
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    The effect of Σ-Π interaction on the oscillator strength of π-π* transition has been investigated in terms of the configuration interaction method considering all singly excited configurations. It has been found that the transition moment associated with π-π* excitation is modified by σ-electrons. The correction term of the transition moment resulting from the Σ-Π interaction can be expressed by the bond index matrix. The present theory has been applied to the calculation of the oscillator strength of benzene and naphthalene derivatives. Agreement between the calculated values and experimental data is satisfactory. The effect of Σ-Π interaction on the transition moment has been demonstrated pictorially.
  • Shingo Araki, Hiromi Ishida, Toshio Tanaka
    1978 Volume 51 Issue 2 Pages 407-410
    Published: 1978
    Released: April 19, 2006
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    Four simple salts and six complex salts of TCNQ\ ewdot radical anion with N,N-dialky1-1,3-dichalcogenacycloalkan-2-iminium cations, (Remark: Graphics omitted.) and (Remark: Graphics omitted.) (n=2 or 3, Y=S or Se, R=Me or Et) were prepared. The electrical resistivity of (Remark: Graphics omitted.) (1.1×104 ohm cm) was more than 10 times lower than other three simple salts ((6.1–8.7)×105 ohm cm). Electronic absorption spectra and magnetic susceptibilities suggest that the latter three involve dimeric (TCNQ)22−, while in the former the interaction between two TCNQ\ ewdot radical anions is weak in the solid state. All the complex salts with compaction samples exhibited the resistivity of 2.4–4.0 ohm cm with very low activation energies (0.018–0.087 eV). Electronic spectra and magnetic susceptibilities show that the interaction between two TCNQ\ ewdot radical anions decreases owing to the implication of neutral TCNQ.
  • Yoshitada Murata, Keiko Nishikawa
    1978 Volume 51 Issue 2 Pages 411-418
    Published: 1978
    Released: April 19, 2006
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    An energy-dispersive X-ray diffractometer using a solid-state detector is constructed for the determination of the liquid structure. It has two merits over the usual angle-dispersive diffractometer, i.e., a higher resolution of the s-value and a wider measurable s-region. The procedure of the data analysis and the results for liquid CCl4 are described. The absorption correction is important in the reflection method. By taking advantage of the energy-dispersive method, it is shown that liquid CCl4 has a long-range correlation at room temperature.
  • Tatsuo Ohgushi, Atsushi Yusa, Kunio Kinoshita, Yoshifumi Yatsurugi
    1978 Volume 51 Issue 2 Pages 419-421
    Published: 1978
    Released: April 19, 2006
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    K12-A zeolite was ion-exchanged with Mg2+, Mn2+, Co2+, Cd2+, or Pb2+, and molecular sieving properties of the resultant zeolites were studied, mainly for PH3 and SiH4. (K, Mg)-A and (K, Mn)-A adsorbed PH3 but not SiH4, and hence are usable as a purifier for SiH4. (K, Co)-A, (K, Cd)-A, and (K, Pb)-A decomposed both PH3 and SiH4, and are unsuitable as an adsorption purifier for SiH4. By using adsorption columns containing (K, Mn)-A or (K, Mg)-A, breakthrough curves were obtained for PH3 in SiH4. The breakthroughs of (K, Zn)-A and (K, Ca)-A columns were also measured for comparison. The breakthrough point increased in the order of (K, Ca)-A<(K, Mg)-A<(K, Mn)-A<(K, Zn)-A. The mechanism of the molecular sieving is discussed. It is concluded that introduced bivalent cations increase the Debye-Waller factor of K+ blocking the windows. A large Debye-Waller factor causes a decrease in the activation energy required for adsorbate molecule to pass through the blocked window.
  • Yoshio Matsunaga
    1978 Volume 51 Issue 2 Pages 422-426
    Published: 1978
    Released: April 19, 2006
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    All the patterns from the isotropic ESR spectrum to the anisotropic one of bis(acetylacetonato)oxovanadium(IV) and related chelates are recorded by employing molten o-terphenyl as a solvent and by changing the temperature above and below the melting point. The results are qualitatively explained in terms of the anisotropic molecular motion and are considered to be evidence for the presence of clusters in the melt. Similar observations are made with some derivatives of 2,4,6-trinitrodiphenylamine, but only partially with m-terphenyl and the 3′-methoxy and 3′-ethoxy derivatives of 2,4-dinitrodiphenylamine. The implications of the results concerning the structure of the melts are discussed.
  • Osamu Ito, Minoru Matsuda
    1978 Volume 51 Issue 2 Pages 427-430
    Published: 1978
    Released: April 19, 2006
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    The transient absorption band appearing at 370 nm by flash photolysis of di-t-butyl dusilfide was assigned to the t-butylthiyl radical. Photolyses of the disulfide solutions containing olefins such as 1,1-diphenylethylene and styrene gave new transient bands in a wavelength region similar to that of the diphenylmethyl radical and benzyl radical, respectively. These new bands can be attributed to the radicals produced by the addition of the thiyl radical to olefins; (Ph)2\dotC–CH2–SR and H(Ph)C–CH2–SR. Kinetic studies including the addition of the thiyl radical to olefins were performed.
  • Haruo Hatakeyama, Tsunetake Fujiyama
    1978 Volume 51 Issue 2 Pages 431-433
    Published: 1978
    Released: April 19, 2006
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    The relative Raman intensities of the v1 line of carbon tetrachloride, the v8 line of acetonitrile, and the v3 line of chloroform were observed in the liquid phase and at various temperatures. The apparent intensity change due to the temperature were explained in terms of the local field effect, the density change, the statistical distribution effect, and the contribution of transition hyperpolarizability in the presence of a non-zero averaged molecular field.
  • Yôichi Iida
    1978 Volume 51 Issue 2 Pages 434-438
    Published: 1978
    Released: April 19, 2006
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    The charge-transfer transition between ion radical molecules is known to take place in solid ion radical salts. The present paper describes some spectroscopic features of the charge-transfer absorptions observed in complex anion radical salts of (Cs+)2(TCNQ)3\ ewdot\ ewdot and (Morpholinium+)2(TCNQ)3\ ewdot\ ewdot. A one-dimensional Hubbard model consisting of equivalent sites with less than half-occupied orbitals was applied to those systems in order to explain the transition energy and the line shape of the charge-transfer absorptions.
  • Koichi Kobayashi, Kenichi Natori, Masamizu Kamaya, Tsunetaka Sasaki
    1978 Volume 51 Issue 2 Pages 439-442
    Published: 1978
    Released: April 19, 2006
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    The adsorbing particle flotation of Fe2+ or Fe3+ and Cu2+ ions was studied by the combined use of bentonite (Bt) and a cationic surfactant, benzylhexadecyldimethylammonium chloride (BHDAC). Fe3+ ions were effectively floated from an aqueous solution by the use of Bt and cationic surfactant in a manner similar to the flotation by the use of sodium silicate and cationic surfactant. Most Fe2+ ions were found to be floated as Fe3+ ions, when the pH was increased by the addition of sodium hydroxide. The maximum floatability of 98% was obtained for Fe3+ under optimum conditions. The pH corresponding to the beginning of flotation of Fe3+ was influenced by the manner in which the pH of the solution was controlled. Cu2+ ions could also be floated, but less effectively than Fe3+ ions. Selective flotation of Fe3+ from the mixed solution of Fe3+ and Cu2+ was attempted and effectively achieved.
  • Kazuo Okada, Okitsugu Kajimoto, Takayuki Fueno
    1978 Volume 51 Issue 2 Pages 443-447
    Published: 1978
    Released: April 19, 2006
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    The thermal decomposition of CF3CN diluted to 0.2 and 0.5 mol% in argon was studied behind incident shock waves over the temperature range 2450–3610 K. Mass spectrometry of the reaction mixture revealed that the decomposition products are C2F6, C2N2, C2F4, and a trace of FCN. The course of the primary process of decomposition, CF3CN+Ar→CF3+CN+Ar, was followed by monitoring the CN(0–1) violet absorption centered at 421.5 nm. It was confirmed that the reaction is still in the low-pressure limit under our experimental conditions. The initial slope of absorption gave the bimolecular rate constant, k=(7.9±3.1)×1015exp[−(94.0±2.8) kcal mol−1RT] cm3 mol−1 s−1. The rate constants obtained are best fitted by the classical collision-theory expression k=λ(Zn!)(ERT)nexp(−ERT) with λ=0.44, n=2, and E=D0(CF3–CN)=102.7 kcal/mol. The mechanism of the overall decomposition was suggested and checked by numerical integrations of the relevant rate equations.
  • Kou Hatada, Yoichi Takeyama, Yosho Ono
    1978 Volume 51 Issue 2 Pages 448-452
    Published: 1978
    Released: April 19, 2006
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    The reaction of γ-butyrolactone and hydrogen sulfide to give γ-thiobutyrolactone over zeolites was studied. Alkaline cation exchanged zeolites have high catalytic activity for the ring conversion, acidic zeolites very low activity. γ-Thiobutyrolactone was obtained in 99% yield with CsY at 330 °C. There is no decay of catalytic activity with time. The reaction kinetics over LiY, NaY, and CsY are expressed by
    r=\frack(aLPL)(aHPH)(1+aLPL+aHPL)2,
    where r is the rate of reaction, PL and PH are the partial pressure of γ-butyrolactone and hydrogen sulfide, respectively, and k, aL, aH are constants. The activation energies for k are 39, 31, and 26 kcal mol−1 with LiY, NaY, and CsY, respectively. Catalytic activity is enhanced by addition of pyridine but almost completely depressed by addition of hydrogen chloride. It is concluded that basic sites play an important role in the ring transformation.
  • Masaru Mitsuishi, Yuzoh Yamaguchi, Naoko Ishii
    1978 Volume 51 Issue 2 Pages 453-455
    Published: 1978
    Released: April 19, 2006
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    The ionic-association reaction of the complex between the Methyl Organic anion and the dodecyltrimethylammonium cation in dioxane–water mixtures has been studied by analyzing the conductivity data. The equivalent conductivities at an infinite dilution and the ionic association constants (KA) have been determined by means of Shedlovsky’s treatment, and they have been compared with those of Methyl Orange (sodium salt). The KA values have been seen to increase with a rise in the temperature and with an increase in the dioxane content. The Walden products have been essentially constant, and they have been found to be comparable to those of Methyl Orange (sodium salt). The data have been analyzed further by the use of the Denison-Ramsey equation, and the ion-ion distance in an associate has been obtained. The ionic-association reaction have been found to increase the heat content and also the entropy.
  • M. V. Ramanamurti, B. V. Apparao
    1978 Volume 51 Issue 2 Pages 456-459
    Published: 1978
    Released: April 19, 2006
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    Adsorption of 1,2-propanediol and methyl cellosolve (isomeric compounds) at Hg–0.10 m KCl (aq) solution interface evaluated through equilibrium double layer capacity measurements indicated congruency of adsorption isotherms with respect to both potential (E) and charge density (σM); applicability of Langmuir’s adsorption isotherm; quadratic dependence of Δ\barG° on E and single stable orientation with the hydrocarbon chain facing the electrode and functional group in solution throughout the coverage region, for both the compounds. Surface excess, standard free energy of adsorption and the anodic shift of Epzc, are greater while the charge corresponding to maximum adsorption is more negative, for methyl cellosolve than for the diol.
  • V. Ponnuraj, M. S. Ramachandran, T. S. Vivekanandam, U. Chandra Singh
    1978 Volume 51 Issue 2 Pages 460-462
    Published: 1978
    Released: April 19, 2006
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    Results on the oxidation of N3 by peroxodisulfate in neutral and acid media are presented. The rate of the reaction is found to be proportional to [N3] and [S2O82−] directly. The product of oxidation is found to be pure nitrogen. The stoichiometry of the reaction is
    S2O82−+2N3=2SO42−+3N2.
    The reaction shows positive salt effect. Thermodynamic activation parameters ΔH and ΔS have been calculated for this reaction. It is observed that H+ ion inhibits the reaction. The mechanism is discussed in terms of the kinetic results.
  • Jörn von Jouanne, Donald A. Palmer, Hartwig Kelm
    1978 Volume 51 Issue 2 Pages 463-465
    Published: 1978
    Released: April 19, 2006
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    The solvatochromic shift and its pressure dependence of the charge transfer band of 2,4,6-triphenyl-pyridinium-N-(3,5-diphenyl-)phenol betaine (ET-values) have been measured together with partial molar volumes of the betaine in a number of solvents.
  • Masazo Kimura, Akira Uehara, Eishin Kyuno, Ryokichi Tsuchiya
    1978 Volume 51 Issue 2 Pages 466-469
    Published: 1978
    Released: April 19, 2006
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    The following four chromium(III) and cobalt(III) double complexes were prepared and the thermal reactions were investigated both isothermally and non-isothermally in the solid-phase: [(Cr or Co)(H2O)(NH3)5][(Cr or Co)(sida)2] where sida denotes N-(2-sulfoethyl)iminodiacetate ion. The double complexes were found to be thermally deaquated to form the homo- and hetero-metal binuclear complexes [(NH3)5(Cr or Co) (sida)(Cr or Co)sida)] in which one of N-(2-sulfoethyl)iminodiacetate ions functions as the bridging ligand between two metal ions. The complexes thus obtained were purified from a 50% HClO4 or a 1 M NaClO4 solution in the forms of the hydrogen salts [(NH3)5(Cr or Co)(sida) (Cr or Co)(sidaH)]ClO4 or the sodium salts [(NH3)5(Cr or Co)(sida)(Cr or Co)(sidaNa)]ClO4.
  • Masashi Goto, Takafumi Hirano, Daido Ishii
    1978 Volume 51 Issue 2 Pages 470-475
    Published: 1978
    Released: April 19, 2006
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    The theory which describes the properties of the 2.5th order derivative of current, e″, vs. the electrode potential, E, curves is presented in response to an imposed ramp signal on a stationary electrode. The 2.5th order differential, e″(t), of the current, i(t), is defined by
    e″(t)≡\fracd2.5dt2.5i(t)=\fracd3dt3\left[\frac1√‾π∫0t\fraci(λ)√‾t−λdλ\ ight].
    The predicted dependences of peak height, peak potential, and peak width on concentration, electron number, and scan rate, etc. have been confirmed experimentally, using the analogue circuit to monitor the electroreductions of Cd2+, Pb2+, Tl+, Zn2+, and Ni2+ on a hanging mercury electrode. It was proved that the proposed technique adds the advantages of further higher resolution and higher sensitivity to those of semidifferential electroanalysis. At the scan rate of 100 mV/s, the signals observed in this technique were about 50 and 8 times larger than those in linear sweep voltammetry for the reductions of Cd2+ and Ni2+, respectively. Sufficient resolution was obtained for the qualitative analyses between Pb2+ and Tl+, between Ni2+ and Zn2+, and between Ni2+ and H+ at pH 1.4 in this technique.
  • Kuninobu Kasuga, Masao Anami, Yasuo Yamamoto
    1978 Volume 51 Issue 2 Pages 476-478
    Published: 1978
    Released: April 19, 2006
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    In the substitution reactions of phenol, benzenethiol, and their sodium salts on the chelate ring of 3-bromo-2,4-pentanedionato metal complexes (metal=iron(III), aluminium(III), and beryllium(II)), benzenethiol was found to be substituted for bromine, while phenol was not substituted under the same conditions. In the case of sodium salts, both sodium phenoxide and benzenethiolate gave substituted products. The UV and PMR data of tris(3-substituted 2,4-pentanedionato)aluminium(III) complexes gave some information on the substituted groups.
  • Yasushi Inoue, Masamichi Tsuji
    1978 Volume 51 Issue 2 Pages 479-482
    Published: 1978
    Released: April 19, 2006
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    In order to understand the cation-exchange behavior of hydrous titanium oxide, the distribution coefficients of various cations were measured as a function of the pH and the ionic strength. The order of selectivity for alkali metal ions is Cs+>Rb+>K+>Na+, for alkaline earth metal ions, Ba2+>Sr2+>Ca2+, and for bivalent transition metal ions, Zn2+>Cu2+>Co2+. From the dependency of the distribution coefficients on the pH, it is concluded that the apparent dissociation constants of the exchanger reported previously are not constant, but gradually decrease with the pH of the medium. By using ammonium chloride and ammonium nitrate solutions as eluents, nearly quantitative separations of 137Cs–133Ba and 137Cs–89Sr were achieved with a relatively small column.
  • Masato Nishizawa, Kazuo Saito
    1978 Volume 51 Issue 2 Pages 483-487
    Published: 1978
    Released: April 19, 2006
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    Square pyramidal [VO(acac)2] (acac, acetylacetonate) undergoes ligand exchange with Hacac[14C] in 1,2-dichloroethane (DCE) without side reactions. The rate is expressed by R=k2[complex] [Hacac], where [Hacac] stands for the concentration of free acetylacetone in enol form. The second order rate constant and activation parameters are 0.071 M−1 s−1 (M=mol dm−3) at −33 °C, ΔH\ eweq=(46.7±1.7) kJ mol−1 and ΔS\ eweq=(−61.9±8.4) J· mol−1 K−1. The deuterium isotope effect is kHkD=1.3±0.2. It appears as if the free Hacac first interacts with the complex as unidentate and the chelation of the unidentate accompanied by proton transfer to the leaving acac is the rate determining step. On addition of a donor solvent the exchange rate decreases, and the extent is correlated with Gutmann’s donor number. The k2, ΔH\ eweq and ΔS\ eweq in 0.06 M dimethyl sulfoxide (DMSO) in DCE are 0.0038 M−1 s−1 at −33 °C, (71.9±10.0) kJ mol−1, and (−4±40) J mol−1 K−1, respectively. The DMSO molecule seems to interact with the intermediate species with a unidentate Hacac and inhibits the associative rate determining step.
  • Toschitake Iwamoto, Mamoru Kiyoki, Yutaka Ohtsu, Yasuko Takeshige-Kato
    1978 Volume 51 Issue 2 Pages 488-491
    Published: 1978
    Released: April 19, 2006
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    A novel series of clathrates Cd(tn)M′(CN)4·2G (M′=Cd or Hg; G=C4H4S, C4H5N, C6H6, or C6H5NH2) were prepared as an analogous series of Hofmann type clathrate. Including the novel series, Hofmann type and the analogous clathrates with a general formulation M(diam)M′(CN)4·2G were classified into five groups according to the combination of the host constituents and the resulting host framework structures as follows: Hofmann type M(NH3)2M′(CN)4·2G with square-planar M′(CN)4, Hofmann-en type Cd(en)NM′(CN)4·2G with ambident en and square-planar M′(CN)4, Hofmann-Td type Cd(NH3)2M′(CN)4·2G with tetrahedral M′(CN)4, en-Td type Cd(en)M′(CN)4·2G with ambident en and tetrahedral M′(CN)4, and tn-Td type Cd(tn)M′(CN)4·2G with ambident tn and tetrahedral M′(CN)4. Their structural features were discussed based on the flexibility of the framework whether it can enclathrate aniline as the largest guest or not.
  • Kazuko Y. Matsumoto
    1978 Volume 51 Issue 2 Pages 492-498
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    Two heteropoly anions, [C6H5AsMo6O21(H2O)6]2− and [(C6H5As)2Mo6O25H2]4−, have been synthesized by the reaction of phenylarsonic acid with molybden um trioxide in an aqueous solution of pH ca. 2. The latter anion has been subjected to crystal-structure analysis as a guanidinium salt, (CN3H6)4[(C6H5As)2Mo6O25H2]·4H2O, and a heteropoly anion with a new type of structure has been established. The crystal is monoclinic with the space group of P21 and cell dimensions of a=13.754(5), b=15.752(7), c=11.900(5) Å, β=115.59(2)°, V=2325.3 Å3, Dm=2.25, Dx=2.28 g cm−3, and Z=2. The formula of the anion has been proved to be [(C6H5As)2Mo6O25H2]4−, which is different from the expected formula, [(C6H5As)2Mo6O24]4−, though the latter had previously been proposed on the basis of a 17O NMR study and an independent X-ray investigation of the methyl derivative had confirmed the existence of the [(CH3As)2Mo6O24]4− anion. The present anion, [(C6H5As)2Mo6O25H2]4−, consists of six MoO6 octahedra, which form a ring with one face-, two corner- and three edge-sharings, the two C6H5AsO3 tetrahedra are attached to the ring from above and below, with their three oxygens shared with molybdenums. The two phenyl groups are oriented upwards and downwards from the ring respectively.
  • Kazuo Fukushima, Takeshi Miyamoto, Yukiyoshi Sasaki
    1978 Volume 51 Issue 2 Pages 499-502
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The 1-allylpyrazole complexes of the general formula Fe(CO)3L (L=substituted 1-allylpyrazoles) have been prepared by the photochemical reaction of Fe(CO)5 in the presence of 1-allylpyrazoles, and characterized by the IR, 1H-, and 13C-NMR spectroscopies. These complexes show a large decrease of ν(C=C) frequency and 1H-and 13C-NMR upfield shifts of the olefinic nuclei compared with free ligands. The upfield shifts of olefinic 1H-NMR spectra are not influenced by the substituent groups on the pyrazole ring, but, so far as the terminal olefinic protons are concerned, the shifts are distinctively decreased on replacement of the allyl by the 2-methylallyl group. The upfield shifts of 13C-NMR spectra substantially parallel those of 1H-NMR spectra in these complexes. On refluxing Fe(CO)3L in a hexane solution containing PPh3, the complex liberates 1-allylpyrazole to give trans-Fe(CO)3(PPh3)2 in a small yield. Some new complexes of general formula M(CO)4L (M=Cr, Mo, or W, L=1-allylpyrazole) have also been prepared for comparison.
  • Yoshiro Terai, Kazuo Saito
    1978 Volume 51 Issue 2 Pages 503-505
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    A new complex salt [Ph4P][PtCl3(S,S-tbn[1,3-3H])] (tbn, trans-2-butene) undergoes racemization and ligand isotopic exchange in acetone containing a large excess of tbn without side reactions. Both rates are expressed by the second order rate equations, R(CD)=K2(CD)[Pt][tbn] and R(IE)=K2(IE)[Pt][tbn], the k2 values being 17.6 and 70.6×10−3M−1s−1 at 8.0 °C, respectively (M=mol dm−3). Individual k2 values for the substitutions without and with inversion of configuration of coordinated tbn are calculated to be 62.0 and 8.7×10−3M−1s−1, respectively, the corresponding ΔH\ eweq and ΔS\ eweq values being 36.3±3.1 and 37.6±2.7 kJ mol−1, and −138±12 and −149±10 J· mol−1 Kr−1. Source of the stereoselectivity appears to consist in the difference in ease of formation of square pyramidal transition state on the nucleophilic attack of tbn upon the complex.
  • N. Ray Chaudhuri, M. K. Dasgupta, S. Mitra, G. K. Pathak
    1978 Volume 51 Issue 2 Pages 506-511
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    Non-isothermal studies of the dehydration of double salt hydrates of the type (NH4)2AB4·M(II)SO4·6H2O and their D2O analogues in solid state were carried out with a derivatograph, where AB4=BeF42− or SeO42−, M(II)=Mg(II), Mn(II), Co(II), Ni(II), Cu(II), or Zn(II). These salt hydrate molecules lost water/heavy water in single or multiple steps upon heating. Intermediate hydrates were isolated and characterised by elemental analysis and IR spectral measurements. The activation energy for each step of dehydration of the salt hydrate was evaluated from the analysis of TG, DTG, and DTA curves of the respective derivatograms. Enthalpy change was evaluated from the DTA peak area and the order of reaction was found to be unity for each step of dehydration. The nature of dehydration was little affected by deuteration. Thermal parameters for the (NH4)2AB4·M(II)SO4·6H2O and their D2O analogues were compared with the salt hydrates, K2AB4·M(II)SO4·6H2O, (NH4)2SO4·M(II)SO4·6H2O and their D2O analogues.
  • Ahmad Sami Shawali, Hamdi Mahmoud Hassaneen, Saleh Almousawi
    1978 Volume 51 Issue 2 Pages 512-515
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    A series of twelve aryl N-(p-nitrophenyl)alkanehydrazonates (I) have been prepared and their thermal rearrangement into N-acyl-N′,N′-diarylhydrazines (II) was investigated. The structures of I and II were derived from their elemental analyses and spectral properties. Hydrolysis of II afforded the corresponding N′,N′-diarylhydrazines. Kinetic experiments have shown that electron withdrawing substituents decrease the rate of the rearrangement whereas electron donating groups increase it. The rate of conversion of I into II was also increased by addition of benzoyl peroxide. A free radical mechanism was proposed to account for the results.
  • Shiva Mohan Verma, Ashok Kumar Singh
    1978 Volume 51 Issue 2 Pages 516-519
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The configurations of the Diels-Alder adducts of maleic anhydride with 2,3-dimethylnaphthalene and 6,6-diphenylfulvene have been investigated by NMR spectroscopy. Restricted rotation and non-planar conformations about the N–N bond in the corresponding N-aminoimide derivatives of the adducts have been employed in solving the structural problem. While the N′,N′-diacetyl system has been shown to be a suitable probe for configurational assignment, N′-acetyl-N′-aroyl-N′-aminoirnide derivatives have been found to be a more diagnostic probe even to simple adducts.
  • Shiva Mohan Verma, Nripendra B. Singh
    1978 Volume 51 Issue 2 Pages 520-523
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    Restricted rotation and non-planar conformations about the aryl C–N bond in ortho substituted arylimides have been studied in order to assign the endo and exo configurations of Diels-Alder adducts, employing the adducts of maleic anhydride with naphthalene and cyclopentadiene as model compounds. The adducts are readily transformed into their o-tolylimide derivatives and the N-o-tolyl probes satisfactorily into the magnetic environment of the cage moiety. In 1-naphthylimide derivatives, the naphthyl group causes splitting in the cage-proton resonances and is found to be more diagnostic for structural assignment.
  • G. Srivastava, P. N. Bhardwaj
    1978 Volume 51 Issue 2 Pages 524-528
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    2-Isopropoxy-4H-1,3,2-benzodioxaborin(I), obtained from isopropyl borate and o-hydroxybenzyl alcohol, reacts with a variety of hydroxy compounds (viz., t-butyl alcohol, phenol, ethane- 1,2-diol, 2-aminoethanol, o-amino phenol) and acetic anhydride to give the corresponding 2-substituted heterocycles. Reactions of (I) as well as other 1,3-dioxa-2-bora heterocycles with bases (viz., ammonia, triethylamine, pyridine, dimethylformamide) show that the electrophilicity of boron decreases in the order: 2-alkoxy-1,3,2-benzodioxaborole>2-phenoxy-4H-1,3,2-benzodioxaborin>(I)>2-alkoxy-1,3,2-dioxaborinane.
    Codisproportionation reaction between bis(4H-1,3,2-benzodioxaborin-2-yl)oxide (obtained directly from boric acid and o-hydroxybenzyl alcohol) and triorganotin hydroxide or oxide yields 2-triorganostannoxy-4H-1,3,2-benzo-dioxyborin. Cleavage and insertion reactions of these compounds have been studied.
  • Seiki Saito, Tatsumi Yabuki, Toshio Moriwake, Kunio Okamoto
    1978 Volume 51 Issue 2 Pages 529-534
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    Solvolysis of 7β-methylbicyclo[3.3.1]non-3β-yl tosylate (1) was carried out in a series of carboxamides, N-methylformamide (NMF), N-methylacetamide (NMA), N,N-dimethylformamide (DMF), and N,N-dimethyl-acetamide (DMA), as solvents. The rate (k1 first-order rate constant) of 1 decreases in the order NMF>NMA>DMF>DMA, a linear free-energy relationship being found between the rates of 1 and those of 1-adamantyl tosylate in acetic acid and 80% ethanol as well as the carboxamides. The products consist of olefin (96%) (exo-7-methylbicyclo[3.3.1]non-2-ene (4) and 3-methylbicyclo[3.3.1]non-2-ene (5)) and small amounts of esters (acetates or formates, 4%). The content of rearranged olefin 5 is considerably less than that of acetolysis (55%) and ethanolysis (55%), decreasing in the order NMF (34%)>NMA(22%)>DMF(13%)>DMA(9%). A linear reactivity-selectivity relationship holds between log k1 and log (%5/%4) for the four carboxamide solvents. The observed kinetic isotope effect (kH/kD=1.01±0.03) for 7α-deuterium-tagged derivative (1-7α-d) in NMF indicates that the σ(C(7)–H)-assisted ionization process for the solvolysis of 1 in the amides is absent. The results are in line with the stepwise mechanism which involves the formation of an intimate ion-pair intermediate followed by competitive processes such as 1,5-hydride shift, syn-El reaction, and nucleophilic substitution by the amide molecules. Substitution by the amide molecule leads to the formation of a cationic imidate, the hydrolysis of which affords the carboxylic esters. It is proposed that the syn-El process via an intimate ion-pair intermediate is affected by the tosylate anion reactivity in each amide solvent and suppressed by the hydrogen bonding of the each amide with the tosylate anion.
  • Kin-ya Akiba, Kiyofumi Ishikawa, Naoki Inamoto
    1978 Volume 51 Issue 2 Pages 535-539
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The reaction of 3-substituted 2-nitrosoimino-2,3-dihydrobenzothiazoles (1) with Grignard-type reagents of 3-substituted 2-imino-2,3-dihydrobenzothiazoles (2) gave azamonomethinecyanines (3) in high yields (71–96%). This is a new type of reaction for the preparation of 3. Hydrolysis of 3 afforded ring-opened disulfides, bis[o-{N-methyl-N-(3-methyl-2,3-dihydrobenzothiazol-2-ylidenecarbamoyl)amino}-phenyl] disulfides, in high yields (78–85%). Formation of by-products is explained by the presence of transnitrosation between 1 and 2 and ring-opening equilibrium of Grignard-type reagent of 2-imino-3-phenyl-2,3-dihydrobenzothiazole.
  • Hideo Tomioka, Hiroshi Fukao, Yasuji Izawa
    1978 Volume 51 Issue 2 Pages 540-543
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The photodecarbonylation of o-benzoquinone to cyclopentadienone at low temperature was monitored by infrared and ultraviolet spectra which showed that the reaction is highly sensitive to substituents. 3,5-Di-t-butyl-o-benzoquinone undergoes clean decarbonylation to give cyclopentadienone under irradiation at −170 °C. Similar irradiation of 4-t-butyl-, 4-methyl-, 3-methyl-, and unsubstituted o-benzoquinones also leads to decarbonylation to cyclopentadienones. However, competitive α-cleavage to bis-ketene becomes important in these systems. Direct spectroscopic observation of the elusive cyclopentadienone was unsuccessful because of the overlapping absorption of the by-product. The infrared spectrum of bis-ketene from 4-t-butyl-o-benzoquinone shows that it exists as a mixture of rotamers, not undergoing thermal interconversion even at −170 °C.
  • Masahiro Minabe, Makoto Suzuki, Takao Ooya, Kazuo Suzuki
    1978 Volume 51 Issue 2 Pages 544-546
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    An unexpected compound, 1,3-di(2-fluorenyl)-1-butene, was formed as the major product, accompanied by meso- and dl-2,3-di(2-fluorenyl) butane as the minor products, in the reaction of 2-(1-bromoethyl)fluorene with silver powder. The structure of the butene was confirmed to be the E form by a comparison of the UV spectra of the related compounds.
  • Jiro Tsuji, Mitsumasa Kaito, Takashi Takahashi
    1978 Volume 51 Issue 2 Pages 547-549
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    8-Acetoxy-1,6-octadiene was oxidized with PdCl2/CuCl/O2 to give 8-acetoxy-6-octen-2-one. Hydrolysis and hydrogenation of the ketone produced 8-hydroxy-2-octanone, which was converted to the tosylate after protection of the ketone. The tosylate was converted into the iodide and bromide. The bromide was converted into the Grignard reagent, and coupled with the iodide by the catalysis of CuI coordinated by 2,2′-bipyridyl to give 2,15-hexadecanedione.
  • Chung-gi Shin, Masato Hayakawa, Takamichi Suzuki, Akira Ohtsuka, Juji ...
    1978 Volume 51 Issue 2 Pages 550-554
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    It is described that alkyl (E)- and (Z)-2-halo (Cl, Br, and I)-acetylamino-2-alkenoate (DHA), obtained by the condensation of alkyl 2-oxoalkanoate with chloro- or bromoacetamide and by halogen exchange from the chlorine of DHA to iodine, are cyclized with ammonia or hydroxylamine to give the (E)- and (Z)-isomers of unsymmetric 3-alkylidene-2,5-piperazinediones and their 1-hydroxy derivatives respectively. Alkyl (E)- and (Z)-2-iodoacetylamino-2-alkenoates were converted into the corresponding acetylamino- and phthalimidoacetylamino derivatives. The configurations of all the DHA and 2,5-piperazinedione derivatives were determined from the NMR spectra data.
  • Shigeru Nishiyama, Yasuhide Ishikawa, Masahiko Yamazaki, Tetsuo Suami
    1978 Volume 51 Issue 2 Pages 555-558
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    An aminocyclitol antibiotic neamine has been modified in its 2-deoxystreptamine moiety by converting the hydroxyl group into an amino group to give three antibiotic amino-deoxyneamines. Their antimicrobial activities were determined against several microorganisms.
  • Yasuhiko Yoshida, Shohei Inoue
    1978 Volume 51 Issue 2 Pages 559-560
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    2-Hydroxycyclohexyl dimethylcarbamate was synthesized quantitatively by a reaction of carbon dioxide, tetrakis (dimethylamido) titanium(IV) and 1,2-epoxycyclohexane.
  • Hiroyoshi Kamogawa, Kuniaki Kubota, Masato Nanasawa
    1978 Volume 51 Issue 2 Pages 561-562
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    Amine exchange reactions between p-vinyl-β-dimethylaminopropiophenone and arylamine hydrochloride provided six novel aromatic Mannich bases bearing a vinyl group which were otherwise hardly accessible. Thus, by refluxingin ethanol-water (1:1),p-vinyl-β-(p-anisidino)-,p-vinyl-β-(p-toluidino)-,p-vinyl-β-(p-hydroxyanilino)-, p-vinyl-β-anilino-, p-vinyl-β-(p-carboxyanilino)-, and p-vinyl-β-(p-nitroanilino)-propiophenones were obtained in 62.0, 55.2, 24.5, 32.0, 47.3, and 29.1% yields, respectively. The Mannich bases thus synthesized underwent ready radical polymerizations to afford the corresponding vinyl polymers, bearing aromatic Mannich base units as pendants.
  • Shinsaku Shiraishi, Tadashi Shigemoto, Shojiro Ogawa
    1978 Volume 51 Issue 2 Pages 563-567
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    Both benzimidazole 3-oxides and 1,2,4-benzoxadiazines were formed in reactions of sterically-stabilized benzonitrile oxides with N-aryl-S,S-dimethylsulfimides, whereas only 1,2,4-benzoxadiazines were produced in reactions of 2,6-unsubstituted benzonitrile oxides. The reactions are thought to proceed via the intermediacy of a nitroso compound formed by the nucleophilic attack of sulfimide on the carbon atom of the nitrile oxide and the subsequent release of dimethyl sulfide. The nitrogen or the oxygen atom of the nitroso group of this intermediate can attack the ortho position of the benzene ring originating from sulfimide to form benzimidazole 3-oxide or 1,2,4-benzoxadiazine, respectively, Conjugation of the nitroso group with the C-aryl group can be attained in s-cis form for the intermediate derived from 2,6-unsubstituted benzonitrile oxide, and thus, exclusive O-attack takes place to afford 1,2,4-benzoxadiazines. On the other hand, conjugation of the nitroso group with the C-aryl group cannot be considered for the intermediate derived from 2,6-disubstituted benzonitrile oxide because of the steric hindrance of the substituents. In this case, the intermediate nitroso compound is either in s-cis or in s-trans form. This causes the formation of both benzimidazole 3-oxide and 1,2,4-benzoxadiazine. Characterization data of benzimidazole 3-oxides are also described.
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