Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 49 , Issue 6
Showing 1-50 articles out of 56 articles from the selected issue
  • Tohru Koike, Kihei Morinaga
    1976 Volume 49 Issue 6 Pages 1457-1461
    Published: 1976
    Released: April 19, 2006
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    The OH(2Σ+2-Π) chemiluminescence in the partial equilibrium region of the H2–O2 reaction in mixtures with H2/O2/Ar=2/2/96, P1=5, 10, 20 Torr was studied in 1250–2000 K incident shock waves. The comparison between the temperature dependence of the OH(2Σ+) emission and that of the computer simulation of the H2–O2 reaction yields the activation energy of the chemical excitation process, assuming the same bi-radical process as former investigators used. The evaluated OH(2Σ+) profile, based on a simulation in which the chemical excitation, radiative, and non-radiative processes are accounted for, depends on the pre-exponential factor of the chemical excitation process. The correlations between the temperature dependence of the evaluated OH(2Σ+) profile and that of the emission profile in the partial equilibrium region gave the pre-exponential factor of the chemical excitation process. Thus, we could estimate the rate constant for O+H+Ar=OH(2Σ+)+Ar to be 1.0×109×exp(−11000 cal⁄RT).
  • Manabu Sen\={o}, Kazutoshi Iwamoto, Teruzo Asahara
    1976 Volume 49 Issue 6 Pages 1462-1464
    Published: 1976
    Released: April 19, 2006
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    The kinetic parameters of the dehydration of Zeise’s salt hydrates, K[PtCl3 (olefin)]·H2O, (olefin; CH2=CH2, CH3CH=CH2, C2H5CH=CH2, n-C3H7CH=CH2 and n-C4H9CH=CH2) and the thermal decomposition of Zeise’s dimers were determined by using DTA and TG. By comparing the kinetic parameters with the data of IR and the enthalpy change of dehydration, it was shown that the important factor in determining the kinetic behavior of the dehydration is an extent of deformation of lattice at the transition state. Similarly, it was suggested that the bulkiness of ligand olefin is an important factor in governing the kinetics of the thermal decomposition reactions.
  • Fumiyuki Watanabe
    1976 Volume 49 Issue 6 Pages 1465-1469
    Published: 1976
    Released: April 19, 2006
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    Conductivity, emf and spectroscopic investigations were made for the dimerization process of Acridine Orange (AO) and for the complex formation of AO with poly(α,L-glutamic acid) (PLG) in water. The increase of the dimer species of AO by adding the neutral salt was quantitatively explained, taking the ionic strength into account. From the emf measurements, the inclusions of Cl into PLG–AO complex were concluded to be negligible, whereas Na+ was included into this complex to a fairly appreciable extent. The association of Na+ with carboxylate groups in the PLG–AO complex was described on the basis of the ordinary law of mass actions. The association constant Ki was unaffected by the presence of AO even in the helical region of PLG. These results strongly support Schwarz’s theory on cooperative binding.
  • Hitoshi Suzuki
    1976 Volume 49 Issue 6 Pages 1470-1474
    Published: 1976
    Released: April 19, 2006
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    The effects of the addition of ethanol and sodium chloride to aqueous solutions of sodium dodecyl sulfate (SDS) were studied by the gel-filtration method. With an increase in the concentration of ethanol, the CMC decreased and then increased after passing a minimum, while the micellar weight increased and then decreased, showing a corresponding maximum. Above about 40 vol% ethanol, no micelle formation was observed. The micellar weight and aggregation number in the presence of ethanol were measured in the SDS concentration range of a constant elution rate of micelles. A decrease in the CMC and an increase in the micellar weight of SDS were observed with an increase in the concentration of NaCl from 0 to 10 mmol/1. The gel-filtration study enabled us to make a direct experimental confirmation of the effects of ethanol and NaCl on the micelle formation of SDS.
  • Yoshihiro Kuroda, Katsunosuke Machida
    1976 Volume 49 Issue 6 Pages 1475-1478
    Published: 1976
    Released: April 19, 2006
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    The optical active normal frequencies and the heats of sublimation of carbon disulfide and sulfur dioxide crystals have been calculated. The interaction between the transition dipoles associated with the infrared active intermolecular modes has been taken into account by introducing coupling terms between the equivalent coordinates of neighboring molecules. The coupling force constants estimated from the infrared absorption intensities explain the observed trend of the factor group splittings of the ν3 mode of carbon disulfide and the ν1 and ν3 modes of sulfur dioxide. The splitting of the ν2 mode of carbon disulfide has been reproduced by taking account of the long range Coulomb interaction between the atomic charges.
  • Akio Yamamoto
    1976 Volume 49 Issue 6 Pages 1479-1485
    Published: 1976
    Released: April 19, 2006
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    Polarizable-ion model calculations are made for optically-active vibrations of five carbonates with calcite structures: calcite, magnesite, dolomite, rhodochrosite, and smithsonite. The fit to the experimental TO-LO splittings of the internal modes is found to be greatly improved by the introduction of ionic polarizabilities. It is also ascertained that the electronic polarizabilities of constituent atoms must be regarded as anisotropic in order to interpret the optical anisotropy. The resulting force constants for non-bonded oxygen-oxygen interactions can give the correct orders of magnitude for the Lennard-Jones potential constants.
  • Takashi Fujikawa, Toshiaki Ohta, Haruo Kuroda
    1976 Volume 49 Issue 6 Pages 1486-1492
    Published: 1976
    Released: April 19, 2006
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    The gas-phase X-ray photoelectron spectra (with MgKα radiation) were observed on acetonitrile, propionitrile, acrylonitrile and fumaronitrile. The ionization potentials were determined for all valence-electron levels of the above molecules by using the data derived from the observed valence-electron bands of X-ray photoelectron spectra and the reported data of ultraviolet photoelectron spectroscopy. It is shown that there is a linear relation between the observed ionization potential (IP) and the CNDO/2 orbital energy (ε): IP=0.61(−ε)+3.2[eV], for σ-orbitals; IP=0.38(−ε)+6.0[eV], for π-orbitals. The observed binding energies of the C ls levels were analyzed by means of the electrostatic potential model and the charge densities calculated by CNDO/2 method. Discussion is given also on the shake-up satellite of core-electron peak.
  • Kazuaki Harata
    1976 Volume 49 Issue 6 Pages 1493-1501
    Published: 1976
    Released: April 19, 2006
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    α-Cyclodextrin(α-CDx) forms 2 : 1 complexes with Methyl Orange sodium salt (MONa) and Methyl Orange potassium salt (MOK). The structures were investigated by the X-ray method. The crystals of both complexes belongs to the orthorhombic space group P21212 with Z=2; the cell dimensions are a=22.099(6), b=16.359(3), and c=8.296(1) Å for the MONa complex, and a=22.120(4), b=16.419(4), and c=8.292(1) Å for the MOK complex. Weak streaks were observed between the layer lines in the oscillation photographs around the c* axis. The structures were determined by using 1566 reflections for the MONa complex and 2544 reflections for the MOK complex, and were refined by the least-squares method to the final R-values of 0.11 and 0.10 respectively. α-CDx is a doughnut-shaped molecule with a large cavity. The crystals have channel structures built up by the stacking of α-CDx rings along the c axes. The Methyl Orange anions are located in the channel with a statistical disorder of four different arrangements. The azo group and the benzene ring are included in the cavity of α-CDx, but the dimethylamino and sulfonato groups protrude from the cavity and are in contact with the adjacent α-CDx rings. The azo group is located at the “neck” of the cavity. The sulfonato group is hydrogen-bonded to the primary hydroxyl groups of α-CDx. No significant structural difference was observed between the MONa complex and the MOK complex.
  • Mitsunobu Nakayama, Moriyuki Nishihira, Yasumasa J. I’Haya
    1976 Volume 49 Issue 6 Pages 1502-1507
    Published: 1976
    Released: April 19, 2006
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    A multi-configuration (MC)-LCAO-MO method is applied to 1,3-butadiene and cyclobutadiene, predicting their molecular geometries and electronic spectra. The molecular ground state geometry, electronic spectrum and stabilization energy of the trans- to the cis-isomer of 1,3-butadiene are predicted to be in good accord with experiments and with those derived from the ordinary semi-empirical SCF-CI method. The results obtained for cyclobutadiene indicate that (a) the Jahn-Teller distortion occurs to favor a rectangular (D2h) form, the stabilization energy being 0.3–0.9 eV depending on approximations, and (b) even in a square (D4h) form a singlet (ground) state is more stable than a triplet state by ca. 0.3 eV. It is also shown that the lowest excited singlet and triplet states (3A2g and 1B1g) in the square form are not subjected to the Jahn-Teller effect. A discussion is given on a possible error in a CI treatment arising when degenerate molecular orbitals are expressed by real coefficients of atomic orbitals.
  • Hiroshi Fujimoto, Tsutomu Minato, Satoshi Inagaki, Kenichi Fukui
    1976 Volume 49 Issue 6 Pages 1508-1511
    Published: 1976
    Released: April 19, 2006
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    The molecular structures of some simple three-membered ring compounds, cyclopropane, cyclopropanone, ethylene oxide and ethylenimine, were studied by means of the orbital interaction between the fragments of a molecule. The relation between the carbon-carbon distance and the bending angle of the carbon-hydrogen bonds in ethylenic part of the three-membered rings is attributed primarily to the greater extent of mixing of the unoccupied π-like MO of ethylenic fragment into the occupied MO’s of rings. The increase in the bending angle as going from ethylene oxide to cyclopropane is interpreted in terms of the interaction of an occupied π-like orbital with the unoccupied α-like orbital of ethylenic fragment through the overlap with the orbital(s) of the residual part of rings. INDO MO and localized orbital calculations support the orbital interaction scheme. The same conclusion is derived also from the electrostatic theory of molecular geometries.
  • Masatoshi Osawa, Aritada Hatta, Kaoru Harada, Wataru Suëtaka
    1976 Volume 49 Issue 6 Pages 1512-1516
    Published: 1976
    Released: April 19, 2006
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    The infrared absorption spectra of ethyl 2-hydroxyimino-3-oxo-3-phenylpropionate, in differently oriented films, formed on Pd metal plates, were measured by using the high-sensitivity reflection method. The thin crystal film A was formed when the solvent was evaporated from the thin liquid film remaining on Pd. On the other hand, the film B resulted from the crystallization of the amorphous solid film which was initially formed on Pd when the liquid film was thick. From the infrared dichroism in the reflection spectra, the molecular orientations in thin films were obtained as follows. In the film A, the ketone C=O and C=N bonds are probably at a pseudo s-cis and are aligned in such a way that the C–C bond connecting the ketone carbonyl group with the C=N group are nearly parallel to the Pd surface. The NO bond is aligned parallel to the metal surface. The ester group is oriented nearly vertical to the metal surface, the C=O bond lying tilted to the surface. In the film B, the ester C=O and NO bonds are aligned nearly perpendicular to the Pd surface, while the ketone C=O bond is not so. The C···C axis of the ester is rather parallel to the surface. The orientation in the thin film A agrees well with the hypothetical chelation model.
  • Tooru Taga, Kenji Osaki
    1976 Volume 49 Issue 6 Pages 1517-1520
    Published: 1976
    Released: April 19, 2006
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    The crystal structure of calcium D-glucarate tetrahydrate has been determined from three dimensional X-ray data, and refined by the least squares method including an anisotropic temperature factor. The crystals are orthorhombic, space group P212121 with a=16.09, b=11.36 and c=6.68Å. The calcium ion is bound to two glucarate molecules and three water molecules. The eight oxygen atoms form the calcium coordination shell of a distorted square-antiprism geometry. The carboxyl group including C(1) of D-glucarate has an eclipsed conformation relative to C(2) and O(2), and is coordinated with one calcium ion through the carboxyl oxygen O(1) and the α-hydroxyl oxygen O(2), and with the other calcium ion through the carboxyl oxygen O′(1) and the hydroxyl oxygens O(3) and O(4). The other carboxyl group including C(6) has an unusual staggered conformation relative to C(5) and O(5), and is not coordinated with calcium ions. However the oxygen atoms of the latter carboxyl group are attached by hydrogen bonds to a number of hydroxyl groups and water molecules, all of which are coordinated with calcium ions.
  • Shizen Sekiguchi, Kinzo Tsutsumi, Haruo Shizuka, Kohji Matsui, Takeshi ...
    1976 Volume 49 Issue 6 Pages 1521-1523
    Published: 1976
    Released: April 19, 2006
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    The electronic structures of 1,1-disubstituted 2,4-dinitronaphthalene Meisenheimer complexes were studied by UV-visible and infrared spectrometry and compared with the results calculated by a semiempirical SCF-MO-CI method. The electronic transitions in the complexes were assigned to those of π-π*. Calculated transition energies and intensities agree well with the observed values. The infrared spectra of the complex indicated that the complex is not a charge transfer complex or a radical anion, but an anionic σ complex.
  • Takashi Okada, Takayuki Fueno
    1976 Volume 49 Issue 6 Pages 1524-1530
    Published: 1976
    Released: April 19, 2006
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    The electronic population in molecular systems is analyzed on the basis of the spin coupling matrix. A proposal is made to define the pair-coupling population which is directly related to the electron pair concept. The theory is applied to the examinations of various types of wave functions used for three-centered two-, three-, and four-electron systems. The results permit clear comparisons of the characteristics of the various wave functions examined.
  • Yukio Zenitani, Kaoru Inoue, Yasushi Kai, Noritake Yasuoka, Nobutami K ...
    1976 Volume 49 Issue 6 Pages 1531-1537
    Published: 1976
    Released: April 19, 2006
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    The molecular structure of (acetylacetonato)(carboxymethyl)(triphenylphosphine)palladium(II) [(acac)-(PPh3)PdCH2COOH] has been determined by means of X-ray diffraction. The crystal belongs to the triclinic system, space group P\bar1, with two formula units in a cell with dimensions of a=10.433(2), b=12.746(2), c=10.224(2) Å, α=106.62(1), β=112.41(2), and γ=75.13(2)°. R=0.032 for 4972 non-zero reflections. The palladium atom, σ-bonded to the methylene group of the acetic acid moiety (Pd–C=2.063(4) Å), has a square-planar geometry. The molecule forms a dimer with the adjacent molecule related by a center of symmetry through an inter-molecular hydrogen bonding between acetic acid moieties, O–H···O=2.621(4) Å.
  • Masaaki Yokoyama, Yoshihiro Endo, Hiroshi Mikawa
    1976 Volume 49 Issue 6 Pages 1538-1541
    Published: 1976
    Released: April 19, 2006
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    Based upon the previously reported experimental results that the exciplex fluorescence of poly (N-vinylcarbazole) films doped with dimethyl terephthalate is partly quenched by an electric field, a model is proposed for the extrinsic carrier photogeneration mechanism. Interaction between a migrating singlet exciton and an electron acceptor (“encounter complex”) produces an electron-hole ion pair having a rather large separation through a charge-transfer process between the components and a thermalization process of the excess energy. This ion pair dissociates into free carriers with Onsager’s probability of escaping the geminate recombination which gives a “relaxed fluorescent exciplex state”. The field dependence of the initial separation of the ion pair is also discussed.
  • Hiroshi Ozawa, Yoji Arata
    1976 Volume 49 Issue 6 Pages 1542-1544
    Published: 1976
    Released: April 19, 2006
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    A method has been proposed to eliminate a baseline oscillation which appears in a correlation NMR spectrum when one wants to observe peaks on the tilted baseline. An interpolation process in correlation NMR spectroscopy is also discussed which minimizes the number of sampling points.
  • Hiroshi Nishikawa, Eishun Tsuchida
    1976 Volume 49 Issue 6 Pages 1545-1548
    Published: 1976
    Released: April 19, 2006
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    The kinetics of poly(acrylic acid)–copper(II) (PAA–Cu) complex formation has been studied by a relaxation method. It was found that the greater stability of PAA–Cu complex than that of a monomeric analog is due to the increase of forward rate constant (kf(PAA)/kf(GA)=4) and decrease of the reverse rate constant (kr(PAA)/kr(GA)=1/4) in the polymer system. The results are explained in terms of an electrostatic effect of poly electrolyte and a conformational change of the polymer ligand.
  • Masayuki Imahashi, Nobuki Takamatsu
    1976 Volume 49 Issue 6 Pages 1549-1553
    Published: 1976
    Released: April 19, 2006
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    Kinetic dissolution experiments of powdered ilmenite and rutile were carried out in sulfuric and hydrochloric acids (0.03–1 M) at temperatures of 40, 65, and 90 °C in order to study the physico-chemical factors and the mechanism for the leaching of titanium and iron from these minerals and rocks under acidic conditions. The dissolution rate of ilmenite was strongly affected by the acidity and temperature of the acid solutions; the rate changes in the H2SO4 solutions were greater than those in the HCl solutions. The dissolution rate of rutile was much slower than that of ilmenite. Ilmenite was decomposed by the dissolution of titanium and iron in a nearly stoichiometric ratio under strongly acidic conditions such as 0.3–1 M. But under milder conditions, such as 0.03–0.1 M at 90 °C, the dissolution rate of titanium dropped rapidly in the initial step and the curved line for iron dissolution was nearly parabolic, suggesting the diffusion of iron through the residual layer of titanium.
  • Kenji Kikuchi, Teisuke Murayama
    1976 Volume 49 Issue 6 Pages 1554-1556
    Published: 1976
    Released: April 19, 2006
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    The anodic reaction of hydrogen peroxide in alkaline solutions has been studied by the polarographic method. Polarograms were recorded in solutions with pH values ranging from 10.0 to 13.5. Hydrogen peroxide in alkaline solutions shows a one-step anodic wave at the dropping mercury electrode. The plot of half-wave potential against pH consists of three segments, each corresponding to a different value of d(E1⁄2)/d(pH): −57 mV for the values of pH below 11.6, −29 mV for the pH range from 11.6 to 13.2, and 0 mV for the values of pH above 13.2 The limiting current is controlled by diffusion. It is concluded that the anodic wave corresponds to the formation of the species [Hg(O2H)(OH)].
  • Noboru Yoshida, Masatoshi Fujimoto
    1976 Volume 49 Issue 6 Pages 1557-1562
    Published: 1976
    Released: April 19, 2006
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    The kinetics of the proton-transfer reactions between hydroxide ion and o-hydroxy azo and o-hydroxy azomethine compounds having a strong O–H···N or an O–H···π intramolecular hydrogen-bond are studied in 50% (v/v) dioxane-water by means of temperature-jump method. The forward and the backward rate constant kf and kr for the overall reactions OH+HA\oversetkf\undersetkr\ ightleftharpoonsH2O+A are evaluated to be in the range between 4.4×104 and 6.1×108 M−1 s−1 and between 1.5×103 and 6.2×104 s−1 respectively. The values of the kf for the azomethines are by several orders of magnitude higher than those of the corresponding azo compounds. The values of kf and kr in dioxane-water are found to be smaller than those in aqueous medium.
  • Kenzo Nagase, Hiroko Yokobayashi, Kozo Sone
    1976 Volume 49 Issue 6 Pages 1563-1567
    Published: 1976
    Released: April 19, 2006
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    The stoichiometry of thermal dehydration of MX2(hmta)2·nH2O (hmta=hexamethylenetetramine; X= Cl, Br, I, NO3, NCS; n=4–10) was established by the TG-DTA methods. The nature of the structural changes caused by complete or partial dehydration was studied on the basis of the accompanying changes in the electronic and vibrational spectra. Anions and hmta in general get into the coordination sphere with a decrease in the number of the coordinated water, but the bulky and weakly basic amine often gets coordinated in the last stage.
  • Yoshie Inomata, Toshio Takeuchi, Takao Moriwaki
    1976 Volume 49 Issue 6 Pages 1568-1572
    Published: 1976
    Released: April 19, 2006
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    Complexes of N,N-bis(2-hydroxyethyl)glycine(BHEG) with a bivalent cation (Cu(II), Ni(II), Co(II), Zn(II), Fe(II), Cd(II), and Pb(II)) have been prepared and investigated by means of infrared absorption spectra, powder surface diffuse reflection spectra, electronic spectra, magnetic susceptibility, and thermal analysis. They can be classified into two types: (A) ML2·nH2O and (B) ML·X·nH2O, (M: metal, L: BHEG, X: Cl or NO3). Ni(II), Co(II), Zn(II), and Fe(II) complexes are of type A, and those of Cd(II) and Pb(II) of type B. In the case of Cu(II) complexes, a blue A type complex (Cu(II)-A) has been prepared from a basic solution and a green B type one (Cu(II)-B) from an acidic solution. From detailed assignments of IR spectra, BHEG is found to have a zwitter ion structure. From magnetic moment data and reflection spectra, we presume that the A type complexes have a trans octahedral structure and the B type complexes a tetrahedral structure.
  • Kazuo Kashiwabara (nee Konya), Kozo Igi, Bodie E. Douglas
    1976 Volume 49 Issue 6 Pages 1573-1578
    Published: 1976
    Released: April 19, 2006
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    Two new cobalt(III) complexes, [Co(acac)(bpy)2]2+ and [Co(acac)(phen)2]2+ (acac=acetylacetonate ion, bpy=2,2′-bipyridine and phen=1,10-phenanthroline) were prepared from the reaction of [Co(CO3)(bpy)2]+ and [Co(CO3)(phen)2]+, respectively, with acetylacetone, and converted to the partially resolved optically active forms using a SP-Sephadex ion-exchange column. [Co(acac)2(bpy)]+ was also resolved partially with a SP-Sephadex column. [Co(acac)2(phen)]+ was resolved with a combination of silver dibenzoyl-d-tartrate and dibenzoyl-d-tartaric acid. The circular dichroism (CD) spectra for these four complexes and for [Co(acac)2(en)]+ and [Co(acac)2(tn)]+ (en=ethylenediamine, tn=trimethylenediamine) were measured. A marked solvent effect was observed in the d-d transition region for the CD spectra of the [Co(acac)2L]+ complexes. The absolute configurations for all these complexes were assigned on the basis of their CD spectra.
  • Takeshi Sakurai, Osamu Yamauchi, Akitsugu Nakahara
    1976 Volume 49 Issue 6 Pages 1579-1584
    Published: 1976
    Released: April 19, 2006
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    Absorption and circular dichroism (CD) spectral behaviors of ternary copper(II) complexes containing two L-α-amino acids or an L-α-amino acid and iminodiacetate (ida), 2,2′-bipyridine (bpy), 2-pyridinecarboxylate (pea), or 2,6-pyridinedicarboxylate (pdea), have been studied comparatively, and synthetic studies have given as crystals the mixed ligand complexes, [Cu(ida)(L-arg)]·2H2O, [Cu(ida)(L-orn)]·2H2O, [Cu(ida)(L-lys)]·1/4H2O, [Cu(pdca)(L-arg)]·H2O, and [Cu(pdca)(L-orn)]·2.5H2O, where L-arg, L-orn, and L-lys denote L-arginine, L-ornithine, and L-lysine, respectively. The CD magnitudes of the systems Cu(ida)(L-arg), Cu(ida)(L-orn), and Cu(ida)(L-lys) were found to be enhanced appreciably as compared with the magnitudes estimated from the values for the corresponding binary systems. These ternary systems showed further magnitude enhancements in 50% aqueous ethanol. The enhanced magnitudes observed for Cu(L-glu)(L-arg), where L-glu is L-glutamate, were also intensified in 10, 20, and 50% aqueous ethanol, whereas they were weakened nearly to the estimated values in aqueous solutions with higher ionic strengths (μ=0.1 and 0.5(NaClO4)). These observations support the view that the pairs of ligands constituting the above ternary complexes are fixed around copper(II) by electrostatic ligand-ligand interactions between the oppositely charged side chains. Pyridine-containing ligands, bpy, pea, and pdea, in the ternary systems with L-α-amino acids affected the signs and the magnitudes of the CD spectra.
  • Morio Suzuki, Toshimi Inai, Ryoka Matsushima
    1976 Volume 49 Issue 6 Pages 1585-1589
    Published: 1976
    Released: April 19, 2006
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    Photoreactions of 2-phenyl-1,3-dioxane (1) and 4,6-O-benzylidene-1,2,3-tri-O-acetylglucopyranose (10) in the presence of benzophenone, acetophenone, or acetone have been studied in both deoxygenated and aerated benzene solutions at room temperature. Photolysis of 1 with ketone in deoxygenated solution gave a dimeric product of 1 (8), cross adduct, and pinacol, while in aerated solution an oxidative ring cleavage product, i.e., trimethyleneglycol monobenzoate (9), was obtained instead of 8, besides smaller amounts of pinacol and cross adduct. The yields of pinacol and cross adduct decreased with the change in ketone in the order benzophenone>acetophenone>acetone, while the yield of 8 or 9 was in the reverse order. Photolysis of 10 with ketone led to results parallel to those of 1: photolysis under nitrogen atomosphere gave pinacol, cross adduct, and a dimeric product of 10 (14), while under bubbling air 4-O-monobenzoate and 6-O-monobenzoate derivatives of 10 were obtained instead of 14, besides pinacol and cross adduct. The effects of temperature, oxygen, and structure on the course of the reaction, to produce dimeric or ring opening products, have been discussed.
  • Kazuya Ohga, Taku Matsuo
    1976 Volume 49 Issue 6 Pages 1590-1594
    Published: 1976
    Released: April 19, 2006
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    Irradiation of 2-pentene-4-olide (I) with 254 nm light afforded three and dimers; two head-to-tail isomers and one head-to-head isomer. The photodimerization proceeds via the lowest triplet state. The quantum yields for the formation of the photodimers were determined as a function of the concentrations of I. Addition of I in the excited state to cyclopentene gave two isomeric cyclobutane derivatives. The photocycloaddition took place more rapidly than the photodimerization of I. The photodimerization was also quenched by anisole, probably through formation of an exciplex between I and anisole.
  • Toshiyuki Fujii, Terutoshi Kimura, Shumpei Sakakibara
    1976 Volume 49 Issue 6 Pages 1595-1601
    Published: 1976
    Released: April 19, 2006
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    His–Gly and Ala–His–Gly were synthesized by the conventional solution methods using various Nα-protected-Nim-tosyl-L-histidines as the key intermediates, and handling conditions of these His(Tos)-derivatives were examined. During treatment of an Nps-peptide with HF, the formation of a strongly photosensitive by-product was observed when anisole alone was used as the scavenger, however the side reaction was completely suppressed when skatole was added to the reaction mixture. In order to evaluate the usefulness of these His(Tos)-derivatives in general peptide synthesis, TRH and LH–RH were synthesized, and both products were obtained in pure form without any difficulty. Thus, it can be emphasized that the use of these His(Tos)-derivatives is efficient and convenient for introducing His-residues into peptides even in solution procedures.
  • Akio Murai, Takeshi Nishimura, Tadashi Masamune
    1976 Volume 49 Issue 6 Pages 1602-1611
    Published: 1976
    Released: April 19, 2006
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    The synthesis of C/D trans- and cis-fused C-nor-D-homo-5α-pregnan-3β-ol 3-acetates (13a and 32) from jervine (1) is described. The configurations of both the compounds and the synthetic intermediates were determined on the basis of chemical and spectral evidence.
  • Akio Murai, Takeshi Nishimura, Tadashi Masamune
    1976 Volume 49 Issue 6 Pages 1612-1621
    Published: 1976
    Released: April 19, 2006
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    The synthesis of C/D trans- and cis-fused C-nor-D-homoandrostan-3β-ol 3-acetates (11a and 34a) from jervine (1) is described. The configurations of both the compounds and the synthetic intermediates are defined clearly on the basis of the chemical and spectral evidence.
  • Tadashi Masamune, Akio Murai, Kouichi Nishizakura, Takako Orito, Satos ...
    1976 Volume 49 Issue 6 Pages 1622-1631
    Published: 1976
    Released: April 19, 2006
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    (1) The relative stabilities between 17-substituted C/D trans- and cis-fused 11-oxoetiojervanes were investigated by treatment of both or either one of these 12-epimeric compounds under equilibrating conditions. The equilibrium ratios thus obtained were estimated qualitatively in terms of the configuration and bulkiness of substituent(s) at C17. (2) The chemical shifts of 19- and 18-methyl protons in a number of etiojervanes were examined collectively. The “principle of additivity” holds satisfactorily for the 19-methyl protons of all etiojervanes, with two exceptional cases, irrespective of the configuration at C12 and also for the 18-methyl protons of 12β-etiojervanes. However, the principle is not applicable for the latter protons of 12α-etiojervanes, suggesting that the D ring would take different conformations depending on the 17-substituents.
  • Koji Ukegawa, Yoshio Kamiya
    1976 Volume 49 Issue 6 Pages 1632-1637
    Published: 1976
    Released: April 19, 2006
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    The oxidation of alcohols and α-substituted toluenes in water, methanol and acetic acid was studied at 60–70 °C in the presence of 0.040 M AIBN. The rate of oxidation of alcohol, kp/(2kt)1⁄2, considerably increases when the alcohol is diluted with an inert solvent. The rate remarkably decreases with the addition of water, methanol or various carboxylic acids. However in the presence of tetralyl hydroperoxide, viz., when the hydroperoxyl radical is replaced by the tetralyl peroxyl radical, no further inhibition effect due to water, methanol or carboxylic acids is observed. The rate of oxidation of 1,4-cyclohexadiene decreases with the addition of water or acetic acid. However in the presence of 0.20 M tetralyl hydroperoxide, no further inhibition effect is observed. The rate of oxidation of 1-phenylethanol decreases with the addition of benzoic acid but not with that of methylbenzoate. The rate of oxidation of (2-chloroethyl) benzene, ethylbenzene and isopropylbenzene does not decrease with the addition of 0.224 M acetic acid, but that of N,N-dimethylbenzylamine, N,N-diethylbenzylamine, benzyl alcohol, 1-phenylethanol and methyl benzyl ether decreases. It is concluded that hydroperoxyl and alkylperoxyl radicals with α-substituents such as hydroxyl, carbonyl, alkoxyl or amino groups undergo deactivation due to hydrogen bonding with water, alcohols and carboxylic acids.
  • Shizen Sekiguchi, Yasushi Hasegawa, Kenji Nakamura, Kohji Matsui, Kens ...
    1976 Volume 49 Issue 6 Pages 1638-1641
    Published: 1976
    Released: April 19, 2006
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    It was found that the molecular weights of adducts in the acid-catalyzed reactions of epichlorohydrin with alcohols obey the Weibull-Nycander distribution but not the Flory distribution. The distribution constants (C=kik0) were found to be smaller than 1, indicating that the reaction rate of the initial stage (k0), i.e., the reaction of epichlorohydrin with a starting alcohol, is greater than the rates of the later stages (ki), i.e., the reactions of epichlorohydrin with its adducts. The results indicate that the reaction proceeds via an “borderline” A-2 mechanism.
  • Hiroshi Kimoto, Hiroshige Muramatsu, Kan Inukai
    1976 Volume 49 Issue 6 Pages 1642-1649
    Published: 1976
    Released: April 19, 2006
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    Phenyl 1,1,2,3,3,3-hexafluoropropyl ketone(I) and 2,2,3-trifluoro-3-(trifluoromethyl)indanone(II) were synthesized by the radical-addition reaction of benzaldehyde to hexafluoropropene. The reduction with NaBH4 and the Grignard reaction with methylmagnesium iodide of these ketones gave the corresponding secondary and tertiary alcohols respectively. A Clemmensen reduction, alkaline hydrolyses, and reactions with hydroxylamine and with diazomethane were also carried out.
  • Shinji Kurokawa, Arthur G. Anderson, Jr.
    1976 Volume 49 Issue 6 Pages 1650-1652
    Published: 1976
    Released: April 19, 2006
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    Thermolysis of p-acetylphenyl 3-guaiazulenecarboxylate (1) results in loss of the ester group. In contrast, thermolysis of phenyl 3-guaiazulenecarboxylate (2) or p-methoxyphenyl 3-guaiazulenecarboxylate (3) gives (i) loss of the ester group, (ii) loss of the 1-methyl group with concomitant rearrangement of the ester group to the 1-position, (iii) interchange of the ester and 1-methyl groups, and (iv) cyclization to 5-isopropyl-7-methyl-1,2-dihydrocyclopenta[c,d]azulen-1-one (9).
  • Masao Tsukayama
    1976 Volume 49 Issue 6 Pages 1653-1655
    Published: 1976
    Released: April 19, 2006
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    A 1,8-dioxaanthracenepropionic acid derivative (5), after being converted into methyl ester-methyl ether (6), was reduced with sodium borohydride to give methyl eriostate (7). Hydrolysis of the ester (7) with alkali afforded eriostoic acid (1). On the other hand, eriostemoic acid (2) was synthesized from methyl eriostemate (10), which was obtained from a 1,5-dioxaphenanthrenepropionic acid derivative (8) via four steps.
  • Kazuhiko Saigo, Anri Morikawa, Teruaki Mukaiyama
    1976 Volume 49 Issue 6 Pages 1656-1658
    Published: 1976
    Released: April 19, 2006
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    Trialkyltin alkoxides, prepared from alcohols and trialkyltin methoxide by azeotropical removal of methanol, are easily oxidized by bromine in the presence of trialkyltin methoxide, a hydrogen bromide captor, to give the corresponding aldehydes or ketones in good yields. Alcohols are oxidized directly in one step to the corresponding carbonyl compounds by utilizing bis(tributyltin) oxide and bromine.
  • Sei-ichiro Imamura, Masaaki Teramoto, Takao Sumi, Hideki Aomi, Hiroshi ...
    1976 Volume 49 Issue 6 Pages 1659-1665
    Published: 1976
    Released: April 19, 2006
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    1,2,3,4-Tetrahydronaphthalene was oxidized in the presence of copper(II) acetate in glacial acetic acid. An addition of lithium chloride which formed complexes with copper(II) ion highly accelerated the reaction, and the initiating process was found to be the decomposition of 1,2,3,4-tetrahydro-1-naphthyl hydroperoxide by the copper(II)–chloride ion complexes. However, only about 8% of the decomposition contributed the initiation, and it was suggested that the larger part of the decomposition proceeded through a non-ionic mechanism. Spectrophotometric and ESR experiments suggested that one of the accelerating effects of the chloride ion was due to its action to decompose the inactive copper(II) acetate dimer and form active copper(II)–chloride ion complexes and that the order of the activity of the complexes was CuCl+<CuCl2<CuCl3,CuCl42−.
  • Masaru Tada, Hiroshi Saiki, Kyo Miura, Hiraku Shinozaki
    1976 Volume 49 Issue 6 Pages 1666-1670
    Published: 1976
    Released: April 19, 2006
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    Three benzyl 1-cycloalkenyl ketones, I–III, were irradiated in the presence of boron trifluoride-diethyl ether (0.05 mol/1) in benzene to give the products V–VII, formed by the bonding between the β-position of αβ-unsaturated ketone and the ortho position of the benzene ring. Benzyl 1-cyclooctenyl ketone (IV) was inactive to the photocyclization because of the preferential geometrical isomerization of the olefin moiety. Trifluoro-acetic acid promotes the reaction exceedingly, but the reaction takes place also in methanol. The reaction in methanol was deduced from quenching experiments to be a triplet process. The reaction takes both singlet and triplet processes when irradiation is carried out in the presence of boron trifluoride–diethyl ether. The participation of the complex between benzyl 1-cycloalkenyl ketone and boron trifluoride is proposed for the singlet process.
  • Akira Amano, Toshio Mukai, Tomoo Nakazawa, Kiyoaki Okayama
    1976 Volume 49 Issue 6 Pages 1671-1675
    Published: 1976
    Released: April 19, 2006
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    Thermal reaction of tropone has been studied at temperatures ranging from 420 to 490 °C and at residence times ranging from 1.5 to 6.9 s using a conventional flow apparatus. Tropone undergoes first-order unimolecular decarbonylation. The value of kinetic parameters for this reaction are evaluated as being: A=1014.2s−1, Ea=54.1 kcal mol−1, ΔS\ eweq=2.8 eu, ΔH\ eweq=52.6 kcal mol−1, and ΔG\ eweq=50.6 kcal mol−1. These values indicate that the decarbonylation takes place by one-step concerted mechanism via a norcaradienone-like transition complex. The latter complex is characterized by a partial transannular C2–C7 bond formation and concerted elongation of C1–C2 and C1–C7 bonds in tropone. The proposed transition complex is in conformity with reported thermal behavior of 1,3,5-cycloheptatriene as well as with molecular orbital symmetry theory.
  • Fujiko Iwasaki, Shuichi Mitamura, Gen-ichi Tsuchihashi
    1976 Volume 49 Issue 6 Pages 1676-1680
    Published: 1976
    Released: April 19, 2006
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    The crystal structure of (+)-1-bromo-2-hydroxy-2-phenylethyl p-tolyl sulfoxide, a major isomer formed by the electrophilic addition of BrOH to (+)-trans-β-styryl p-tolyl sulfoxide (1), has been determined by the X-ray diffraction method. The crystal is hexagonal; space group, P62; a=15.61, c=10.82 Å, and Z=6. The final R value is 0.079. A helical chain of the hydrogen bond between hydroxyl and sulfinyl groups (O···O, 2.63 Å) is formed around the threefold screw axis. The absolute configuration has been determined to be Ss, Sc(1), Sc(2) from the Mo Kα anomalous scattering of bromine and sulfur atoms. The bromine atom is gauche to the sulfinyl oxygen across the C(1)–S bond and trans to the hydroxyl oxygen across the C(1)–C(2) bond. Based on the established absolute configuration of the title compound, a mechanism which involves the preferential formation of an intermediary bromonium ion is proposed for the addition of BrOH to 1.
  • Hajime Yoshida, Nobuyuki Sugita, Kiyoshi Kudo, Yoshimasa Takezaki
    1976 Volume 49 Issue 6 Pages 1681-1685
    Published: 1976
    Released: April 19, 2006
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    Benzaldehyde was obtained in good yields by the formylation of iodobenzene with carbon monoxide and hydrogen catalyzed by palladium(II) chloride in a pyridine solution. The effect of following variables on the rate of producing benzaldehyde was examined kinetically : initial catalyst and iodobenzene concentrations, partial pressure of carbon monoxide and hydrogen, and temperature. A probable reaction mechanism via formyl- and benzoyl-palladium(II) intermediates is discussed on the basis of this kinetic study.
  • Juji Yoshimura, Kazutoshi Mikami, Ken-ichi Sato, Chung-gi Shin
    1976 Volume 49 Issue 6 Pages 1686-1689
    Published: 1976
    Released: April 19, 2006
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    Stereoselectivities in the Grignard, diazomethane and nitromethane reaction of methyl 3-O-benzoyl-4,6-O-benzylidene-α-D-arabino-hexopyranosid-2-ulose (1) were examined. In contrast to the Grignard reaction of 1 using methylmagnesium iodide to give a single 2-C-methyl derivative (4), the diazomethane reaction followed by reduction afforded another epimer (6). The nitromethan condensation product (10) of 1 was converted into the corresponding 2-C-acetaminomethyl derivative (13). The NMR spectrum of 2-O-acetate of 4 and comparison of the optical rotations of 4, 6, 10 and 13 in cupraramonium solution indicated that 4 and others have D-gluco-and D-manno-configuration, respectively. Discussions were made on the stereoselectivties of these reactions.
  • Hiizu Iwamura, Yuzo Imahashi, Katsuhiko Kushida, Kiyoshi Aoki, Shiroh ...
    1976 Volume 49 Issue 6 Pages 1690-1696
    Published: 1976
    Released: April 19, 2006
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    When methyl diazoacetate is allowed to react thermally with dibenzyl, benzyl phenyl and benzyl ethyl ethers, insertion into the benzylic carbon–oxygen bonds takes place inter alia to give PhCH2CH(OR)CO2CH3(3, R=PhCH2, Ph, and CH3CH2, respectively). Strongly polarized signals due to the insertion products 3 were observed in the 1H and 13C NMR spectra of the reacting mixture. Application of Kaptein’s rules to the CIDNP signals demonstrates the formation of 3 by the cage recombination of radical pairs ‾PhCH2··CH(OR)CO2CH3 (2). Product analyses by VPC have also been performed and escape products toluene and ROCH2CO2CH3 (4) inherent to the radical pairs were detected. In the reaction with benzyl ethyl ether, 4 (R=PhCH2) without noticeable CIDNP is produced about six times more than 4 (R=CH3CH2). No methyl α-benzyloxybutyrate is formed. The results indicate that the ethyl group is more easily cleaved than the benzyl via a non-radical path. Formation of an ylide intermediate (PhCH2)R\overset⊕O–\overset\ominusCHCO2CH3 (1, R=CH3CH2) followed by the Hoffmann type β-elimination of ethylene is the most reasonable explanation. Homolysis of the same ylide 1 is considered to give the radical pair 2 (R=CH3CH2). A similar process appears to lead solely to radical pairs 2 (R=PhCH2, Ph) in the case of ylides lacking β-hydrogen. The potentiality of this ylide mechanism in the reactions of ethers is discussed.
  • Masayuki Yoshida, Hiroyuki Kaneko, Akihide Kitamura, Tomiyasu Ito, Kun ...
    1976 Volume 49 Issue 6 Pages 1697-1700
    Published: 1976
    Released: April 19, 2006
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    Light induced tritiation of benzonitrile with diethylamine[N3H] or triethylamine-tritiated water was studied with respect to quenching of benzonitrile fluorescence by the amines and the tritium distribution in the nucleus. A mechanism involving an exciplex possessing charge transfer nature was proposed.
  • Jiro Tsuji, Katsuhiko Tsuruoka, Keiji Yamamoto
    1976 Volume 49 Issue 6 Pages 1701-1702
    Published: 1976
    Released: April 19, 2006
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    A simple preparation of 1-octen-3-ol so called Matsutake alcohol using a butadiene telomer is described: selective hydrogenation of the terminal double bond of 2,7-octadienyl acetate gave 2-octenyl acetate which was converted via palladium-catalyzed allylic rearrangement and hydrolysis into 1-octen-3-ol.
  • Keizo Ogino, Wataru Agui
    1976 Volume 49 Issue 6 Pages 1703-1708
    Published: 1976
    Released: April 19, 2006
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    The removal of simply constituted oily soil from a low-energy surface such as polypropylene (PP) has been examined in aqueous solutions of sodium dodecylbenzenesulfonate and its builders. Oleic acid, olive oil, lauryl alcohol, oleyl alcohol, and liquid paraffin were used as model oily soils. Rolling-up was observed in all the soils except oleyl alcohol and liquid paraffin. The rolling-up of the soil occurred in the contact angle range of 0°<θ<90°(θ is contact angle) when the soil was removed incompletely from PP. Apparent activation energies for rolling-up were derived, i.e., 8 kcal/mol for oleic acid and 11.9 kcal/mol for olive oil. Complexes were formed for oleic acid, lauryl alcohol, and oleyl alcohol. The effects of the surfactant in various concentrations at various temperature, and with various builders were studied in view of the interfacial tension and the contact angle.
  • Tsuguhiro Kaneda, Chuji Katayama, Jiro Tanaka
    1976 Volume 49 Issue 6 Pages 1709-1710
    Published: 1976
    Released: April 19, 2006
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    The crystal and the molecular structure of the titled compound was investigated by the X-ray diffraction method. The absolute configuration was determined by the Bijvoet method as 1R4S5R8S.
  • Kunio Tamaki, Mitsuyoshi Kushida, Y\={o}ko Ohara
    1976 Volume 49 Issue 6 Pages 1711-1712
    Published: 1976
    Released: April 19, 2006
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    The viscosity B coefficients of the Jones-Dole equation for di-n-alkylammonium chlorides (methyl to butyl) and tri-n-alkylammonium chlorides (methyl to propyl) in water at 25 °C were determined, and the effect of structural changes in the solvent water induced by the alkyl-substituted ammonium ions is discussed.
  • Tsuneo Matsuda, Isao Seto, Toyosuke Tanaka
    1976 Volume 49 Issue 6 Pages 1713-1714
    Published: 1976
    Released: April 19, 2006
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    The catalytic hydroboration of ethylene with diborane to triethylborane in the gas phase was studied in the presence of various catalysts. The acidity of catalysts and the reaction activity were measured; the increase in the activity can be related to surface acidity of the catalysts.
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