Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 55 , Issue 3
Showing 1-50 articles out of 74 articles from the selected issue
  • Yasuhiro Okuri, Yoshiaki Ogo
    1982 Volume 55 Issue 3 Pages 645-646
    Published: 1982
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The mechanochemical behavior of methacrylamide was investigated at room temperature and at static pressures of up to 15 kbar. The determinations of the IR spectrum, the ESR signal, the X-ray diffraction pattern, and the molecular weight by GPC apparatus confirmed that the reaction products were amorphous polymethacrylamide. The reaction of methacrylamide under conditions of high pressure combined with simultaneous shear deformation(HP+SSD) is a free radical polymerization. The concentration of radicals of polymethacrylamide and the relation between the conversion and the shearing degree suggest that an acrylamide crystal is less stable than one of methacrylamide. Methacrylamide was not reached 100% conversion even at about 2π rad shearing.
  • Yasuhiro Okuri, Yoshiaki Ogo
    1982 Volume 55 Issue 3 Pages 647-650
    Published: 1982
    Released: June 27, 2006
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    The mechanochemical behavior of acrylamide–methacrylamide (AA–MAA) and acrylamide–propionamide (AA–PA) solid solutions was investigated at room temperature and at static pressures of up to 15 kbar. The AA–MAA solid solution was copolymerized under the experimental conditions. On the other hand, the reaction product of AA–PA solid solution was an amorphous homopolymer of polyacrylamide. That is, the mechanochemical reaction of AA–PA solid solution proceeded only in the acrylamide area by a free radical mechanism. The mechanical behavior of both solid solutions was also discussed.
  • Yusaku Ikegami, Takashi Muramatsu, Toyonobu Asao
    1982 Volume 55 Issue 3 Pages 651-653
    Published: 1982
    Released: June 27, 2006
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    The hyperfine splitting constants for the 8,8-dicyanoheptafulvene anion radical generated electrolytically at low temperature indicate that the unpaired spin belongs to an a2 orbital of the group C2v. Its 4,5-benzo derivative gives a stable anion radical by reduction with alkali metals. The odd electron belongs to a b2 orbital.
  • Yoshihiro Aikawa, Haruhisa Shimoda, Kenkichiro Kobayashi, Akira Takaha ...
    1982 Volume 55 Issue 3 Pages 654-659
    Published: 1982
    Released: June 27, 2006
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    An electrohydrodynamic dissipative structure appearing in a suspension system of TiO2 particles in organic solvents is analyzed from a viewpoint of thermodynamics. This analysis gives rather a general explanation for electrohydrodynamic instability caused by unipolar injection and for that caused by bipolar injection. Dimensionless parameters which are the criteria of the hydrodynamic instability are given as RV⁄ημ and R2V2nqμηc2 respectively for the former and latter cases. The lattice constant of the hexagonal dissipative structure is derived to be proportional to the thickness of the liquid layer.
  • Yoshio Hori, Shin Suzuki
    1982 Volume 55 Issue 3 Pages 660-665
    Published: 1982
    Released: June 27, 2006
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    Cathodic reduction of carbon dioxide at a mercury pool electrode was investigated in aqueous solutions of NaHCO3, NaH2PO4–Na2HPO4, NaCl, NaClO4, Na2SO4, LiHCO3, and KHCO3 as well as their combinations. The reaction product was confirmed to be HCOO by a qualitative spot test. HCOO was quantitatively analyzed by a permanganate titration. The partial current densities of HCOO formation (ic) and H2 evolution (iH) were calculated. In the present paper, relationships between electrode behavior and solution properties, some of which have been qualitatively described in previous papers, are quantitatively clarified as follows. The electrode potential Ec for constant ic (0.5 mA/cm2) remains constant irrespective of pH and anions in the pH region of 2.4 to 7.8, whereas the potential EH for constant iH (0.5 mA/cm2) varies linearly with a slope of 125 mV/pH. The present experimental results verify Eyring et al.’s presumption that in a relatively high overvoltage region (region 2) the cathodic reduction of CO2 at Hg proceeds with the charge transfer to CO2 as the rate determining step. CO2 reduction and H2 evolution are concluded to proceed independently at the Hg electrode. The dependence of Ec on electrolyte concentration is interpreted in terms of the diffuse double layer theory. The effect of cation species on Ec also is discussed.
  • Masamichi Fujihira, Yoshiharu Satoh, Tetsuo Osa
    1982 Volume 55 Issue 3 Pages 666-671
    Published: 1982
    Released: June 27, 2006
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    The effect of pH and Cu2+ ions on the heterogeneous photocatalytic oxidation of toluenes by H2O2 formed from dissolved O2 in the presence of illuminated TiO2 powders, i.e. “the photo-Fenton type reaction,” was investigated. At low and high pH, a total amount of products increased drastically compared with that of the additive free system (pH 7). In the acidic region (aqueous H2SO4), side-chain oxidation prevailed over cresol formation and benzaldehyde was formed quite selectively at pH 1. Oxidation of the side chain in preference to hydroxylation of aromatic ring was also observed in the alkaline region (aqueous NaOH). By adding Cu2+ ion to the aqueous H2SO4 (pH 1 and 2), the yield of benzaldehyde increased further and cresols, benzyl alcohol, and bibenzyl were formed newly in high yields. At high Cu2+ concentrations (pH 2), the cresol formation in preference to the side-chain oxidation was attained. The observation was in good agreement with the Fenton reaction reported in which Cu2+ and Fe3+ ions are added as oxidants for the intermediate products, such as hydroxycyclohexadienyl and benzyl radicals, formed by HO· attack to toluene. Cu2+ ion was more preferable to Fe3+ ion as the oxidant, since “short circuiting” by Cu2+ due to the reversible redox reaction at semiconductor particles was much lower than that by Fe3+. By adding a large amount of Cl ions to the Cu2+–H2SO4 aqueous system, no oxidation of toluene resulted.
  • Hideki Masuda, Akira Fujishima, Kenichi Honda
    1982 Volume 55 Issue 3 Pages 672-675
    Published: 1982
    Released: June 27, 2006
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    The photoacoustic spectroscopic technique was used to study in situ cathodic decomposition of CdS and ZnO semiconductor electrodes and electrochemical deposition of metal ions (Cd2+ and Zn2+) on the semiconductor electrodes.
  • Taro Eguchi, Michihiko Kishita, Hideaki Chihara, Gen Soda
    1982 Volume 55 Issue 3 Pages 676-679
    Published: 1982
    Released: June 27, 2006
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    Spin-lattice relaxation times of proton and fluorine nuclei in solid CHF3 were measured by the pulsed magnetic resonance technique between 7 and 116K. In 1H resonance, non-exponential recovery of magnetization was clearly observed. T1 data as well as magnetization recoveries were interpreted in terms of intramolecular magnetic dipole interactions between like spins and also between unlike spins, which are modulated by the isotropic reorientation of a whole molecule. A calculation of the temperature dependence of T1 was made by using an activation energy of 17kJ mol−1 and a pre-exponential factor of 1.0×10−16 s for the motion, yielding results in agreement with the present experimental results.
  • Akio Takenaka, Yoshio Sasada
    1982 Volume 55 Issue 3 Pages 680-686
    Published: 1982
    Released: June 27, 2006
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    Crystal of adenine :phthalic acid (3:1) complex hexahydrate were obtained from an aqueous solution containing equimolar amounts of adenine and N,N-phthaloyl-DL-glutamic acid. The space group is P\bar1 with unitcell dimensions of a=14.232(2), b=16.730(2), c=7.336(1) Å, α=78.97(1), β=96.14(1), and γ=68.99(1)°. The structure was solved by the direct method and its parameters were refined by a block-diagonal least-squares technique. The two carboxyl groups of the phthalic acid are dissociated and they are hydrogen-bonded to the amino group and the protonated N(1) of the two adeninium monocations. The geometrical characteristics in adeninium monocations are explained with the electronic structures perturbed by the surroundings. A typical feature of the C–H···N hydrogen bond is observed between the adeninium cations. The third adenine molecule is neutral and disordered. A comparison of the dissociation constants of the related compounds suggests that the protonation of adenine occurs when the hydrogen bonds are formed between the carboxyl group of acidic amino acid residue in protein and the unpaired adenine base in nucleic acid.
  • Ikuo Abe, Katsumi Hayashi, Mutsuo Kitagawa
    1982 Volume 55 Issue 3 Pages 687-689
    Published: 1982
    Released: June 27, 2006
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    Freundlich’s adsorption constants of 17 amino acids from aqueous solutions onto an activated carbon have been determined and correlated with various physical constants. A good linear relationship is obtained between the adsorption constants and such physical constants as the molecular refraction and the parachor. The adsorption isotherms of amino acids can be predicted from the molecular refraction or the parachor alone.
  • Tohru Koike, Kihei Morinaga
    1982 Volume 55 Issue 3 Pages 690-695
    Published: 1982
    Released: June 27, 2006
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    The UV absorption measurements at 216 nm were carried out for two shock-heated mixtures, 1.5 and 2.0% i-C4H10 diluted in Ar, in the temperature range of 1300–1800 K, and at an atmospheric pressure of about half. From the initial absorption rise attributed to the CH3 growth, the rate constant of the initiation reaction, i-C4H10=CH3+i-C3H7, was evaluated as k=1012.8±0.5exp[−(60.8±4.6) kcal/RT]/s−1. A comparison between the k value so derived and the formerly reported values was made. A computer modeling using a 39-reaction mechanism could reproduce the absorption at the early stage of the reaction at temperatures lower than 1550 K, whereas the modeled absorption was smaller than the measured at much high temperatures. The absorption by C3H5 (allyl radical) must be taken into account in order to lessen this difference.
  • Kimihiko Ogihara, Minoru Ueno, Kenjiro Meguro
    1982 Volume 55 Issue 3 Pages 696-698
    Published: 1982
    Released: June 27, 2006
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    An effect of a mixed surfactant of SDS and homogeneous octaethylene glycol dodecyl ether (8ED) upon the stability and particle size of an octane-in-water emulsion was studied. The mixed surfactant solutions were found to exhibit equi-interfacial-tension over a wide concentration region of a mixed 8ED; the SDS concentrations were 6, 8, and 20 mmol dm−3. The emulsion prepared by using mixed surfactant solution in such a concentration region showed a similar mean particle size. When SDS concentration was kept at 8 or 20 mmol dm−3, The emulsions prepared by the mixed surfactant solutions had similar stability, independently of the mixed 8ED concentration. In the presence of 1 mmol dm−3 of SDS, the stability of the emulsions increased with the increasing concentration of mixed 8ED. In the case of SDS concentration of 6 mmol dm−3, the emulsion was most stable at 1×10−3 mol dm−3 of mixed 8ED.
  • Tetsuo Sakai, Gin-ya Adachi, Takeshi Yoshida, Shin-ya Ueno, Jiro Shiok ...
    1982 Volume 55 Issue 3 Pages 699-703
    Published: 1982
    Released: June 27, 2006
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    A cubic-tetragonal phase transformation of EuC2 was observed at 623 K. The phase transition temperatures of metal dicarbides (MC2) were discussed in terms of the band structure proposed by previous authors. The compound EuC2 was a ferromagnet with a zero field curie temperature of 20 K, which was close to the value expected from the Curie temperature vs. nearest neighbor Eu–Eu distance relation for the Eu chalcogenides. The solid solutions, LaxEu1−xC2, became ferromagnetic at low temperatures over the whole composition range, while the solid solutions, GdxEu1−xC2, have continuously changed the kind of magnetic order from ferromagnetic to antiferromagnetic. All the effective moments obtained for RxEu1−xC2 were in good agreement with the theoretical values of Eu2+ and R3+ contained. The electrical resistivities of EuC2 and its solid solutions had a sharp peak near the Curie temperature. When magnetic field was applied, the peak became broader and shifted to higher temperature.
  • Masatoshi Hirayama, Kenji Akutsu, Kazuko Fukuzawa
    1982 Volume 55 Issue 3 Pages 704-708
    Published: 1982
    Released: June 27, 2006
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    The 13C shifts of 1- and 2-naphthylamines induced by Gd(fod)3 and Gd(dpm)3 were shown to consist predominantly of a contact contribution, based on the fact that these shifts excellently correlate with the hyperfine coupling constants obtained from the graphical analysis of 13C shifts induced by other Ln(fod)3, where Ln is La, Pr, Nd, Sm, Eu, Dy, Ho, Er, or Yb. It was found from the INDO MO calculations of the spin densities of ligand moieties that these Gd-induced shifts parallel the spin-density distribution of the naphthylmethyl radical better than that of the naphthylamine cation radical and that these shifts are best interpreted in terms of the superposition of the β-spin of the naphthylmethyl radical and the α-spin of the naphthyl radical. This may suggest that a direct spin transfer occurs through space from Gd3+ to the amine molecule, in addition to the normal through-bond delocalization via the N-lone pair.
  • Kazutoshi Iwamoto, Shun-ichi Mitomo, Jun-ichi Fukide, Tadashi Shigemot ...
    1982 Volume 55 Issue 3 Pages 709-712
    Published: 1982
    Released: June 27, 2006
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    Rhythmic crystallization behavior of methyl mesitylcarbamate from chloroform solutions under appropriate conditions was found. Effects of temperature, evaporation rate of solvent, and sample weight per area on this behavior are studied in detail, and the qualitative explanation based on the autocatalytic branching process is proposed.
  • Isao Ando, Kikujiro Ujimoto, Hirondo Kurihara
    1982 Volume 55 Issue 3 Pages 713-716
    Published: 1982
    Released: June 27, 2006
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    The deprotonation rates of the conjugate acids of 2,2′-bipyridine and pyridine, and the protonation rates of 2-aminopyridine and 4-aminopyridine were measured in non-buffered aqueous solution by means of a stopped-flow pH jump method. These pyridine derivatives showed quite slow protolytic behavior, similar to that of 1,10-phenanthroline and cyclopentadienes: the deprotonation rate constants of conjugate acids of 2,2′-bipyridine and pyridine are (4.8±0.7)×10−1 and (6.0±2.2)×10−2 s−1, respectively. The deprotonation rates of barbituric acid and acetylcyclopentadiene as authentic samples were also measured. Their deprotonation rate constants are in good agreement with the literature values, this demonstrates the validity and the applicability of the stopped-flow pH jump method. This method is superior to the NMR method for the determination of the protontransfer rates of azaaromatic compounds.
  • Masaaki Katsumata, Kazuo Kasatani, Masahiro Kawasaki, Hiroyasu Sato
    1982 Volume 55 Issue 3 Pages 717-720
    Published: 1982
    Released: June 27, 2006
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    Resonance Raman spectra of 3,3′-diethylthiacarbocyanine iodide–sodium dodecyl sulfate (SDS) system are characterized by [SDS]-dependent change of band intensities. The change was much larger than that accompanied with the shift of monomer-dimer equilibrium in the aqueous solution. The spectra for [SDS]<<critical micelle concentration (cmc) resemble that of the dye in the solid state, indicating the highly-aggregated state of the dye caused by the interaction with the detergent.
  • Isao Ikemoto, Yong Cao, Masamichi Yamada, Haruo Kuroda, Issei Harada, ...
    1982 Volume 55 Issue 3 Pages 721-725
    Published: 1982
    Released: June 27, 2006
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    The bromine-doped polyacetylenes were studied by X-ray photoelectron spectroscopy. The IR, Raman, and mass spectra were also measured. We find that below the doping content at which the electrical conductivity shows the maximum, bromine content is higher in the surface region than in the bulk. The C ls peak of X-ray photoelectron spectrum is composed of at least two components with the splitting of about 1.7 eV. The relative intensities of two components change with bromine content. The higher-binding-energy component of C ls peak is attributed to positively charged carbon atoms in the metallic domains where dopant is highly concentrated, and the lower-binding-energy component to carbon atoms in the undoped low-conductive domains. The amount of charge transfer in the metallic domain is estimated to be about 0.3|e| per carbon atom. A possible reaction mechanism of bromine with polyacetylene is discussed.
  • Tetsuo Fukasawa, Isamu Kawasuji, Toshiaki Mitsugashira, Akiko Sat&ocir ...
    1982 Volume 55 Issue 3 Pages 726-729
    Published: 1982
    Released: June 27, 2006
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    Stability constants (β1 and β2) of the chloro and bromo complexes of tervalent Sm, Eu, Gd, Tb, Ac, Am, Cm, Bk, and Cf were determined by a solvent extraction method under the conditions of ionic strength and acidity to be 3.0 and 0.15 M (1 M=1 mol/dm3), respectively. Stability constants obtained were discussed with respect to the formation mechanism. A much larger contribution from the inner sphere complex formation was observed in chloro complexes than bromo complexes on tripositive actinoids.
  • Toyoaki Aoki, Makoto Munemori
    1982 Volume 55 Issue 3 Pages 730-732
    Published: 1982
    Released: June 27, 2006
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    Iron(II) hydroxide stoichiometrically reduces CrO42− to chromium(III) in alkaline solutions of pH 8 or above. This reduction was finished in less than one minute even at 5 °C. Although chromium(III) dissolves as CrO2 above pH 9.5, it did not dissolve in the presence of iron(III) hydroxide which had resulted from the oxidation of iron(II) hydroxide.
  • Hidenari Inoue, Takashi Kawai, Masaki Nagao, Saburo Yanagisawa
    1982 Volume 55 Issue 3 Pages 733-737
    Published: 1982
    Released: June 27, 2006
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    A series of compounds of the type M3[Fe(CN)5CO]2·xH2O (M=Mn, Co, Ni, Cu, and Zn) have been studied by means of the X-ray diffraction powder patterns, magnetic measurements, infrared, electronic, and M\ddotossbauer spectra. Three compounds M3[Fe(CN)5CO]2·xH2O (M=Mn, Co, and Ni) crystallize in the face-centered cubic system. Copper compound Cu3[Fe(CN)5CO]2·18.5H2O belongs to the tetragonal system, zinc compound Zn3[Fe(CN)5CO]2·13.5H2O being amorphous. The structure of these compounds is described as a three-dimensional framework of two octahedral coordination units FeC6 in the low spin state and MN10⁄3O8⁄3 in the high spin state. The back donation in the Fe(CN)5CO3− moiety is enhanced by the bridge formation through CN and CO ligands, i.e. upon the formation of M3[Fe(CN)5CO]2·xH2O from the corresponding sodium salt.
  • Yasuo Arai, Tamotsu Yasue, Norifumi Nagata, Hiroaki Shiino
    1982 Volume 55 Issue 3 Pages 738-741
    Published: 1982
    Released: June 27, 2006
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    Among the three modifications of calcium sulfite hemihydrate, two of them, hexagonal β-CaSO3·1/2H2O with a rhombohedral lattice and γ-CaSO3·1/2H2O with a simple triangular hexagonal lattice, were found in the authors’ recent work. By heating α- and/or γ-hemihydrate at 330–360 °C in a nitrogen atmosphere, the orthorhombic anhydrate α-CaSO3 was formed, with lattice constants of 6.472, 15.93, and 23.44 Å for a, b, and c respectively, while the body-centered tetragonal anhydrate β-CaSO3, with lattice constants of 15.68 and 19.44 Å for a and c respectively, was formed by heating the β-hemihydrate. The dehydration of three hemihydrates and the hydration of two anhydrates were discussed. The phase relationships in the CaSO3–H2O system were summarized as follows:
    α-CaSO3·1⁄2H2O\oversetDehydration (360°C)\undersetHydration(30°C)\ ightleftarrowsα-CaSO3+1⁄2H2O;
    β-CaSO3·1⁄2H2O\oversetDehydration (360°C)\undersetHydration (30°C)\ ightleftarrowsβ-CaSO3+1⁄2H2O;
    γ-CaSO3·1⁄2H2O\xrightarrowDehydration (330°C)α-CaSO2+1⁄2H2O;
    γ-CaSO3·1⁄2H2O\xrightarrowTransformation (in water at 20°C)
    β-CaSO3·1⁄2H2OO\xrightarrowTransformation (in water at 20°C)α-CaSO3·1⁄2H2O.
  • Yoshikazu Yamamoto, Michiyuki Sugita, Kazumasa Ueda
    1982 Volume 55 Issue 3 Pages 742-745
    Published: 1982
    Released: June 27, 2006
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    A rapid and precise X-ray fluorescence spectrometry is proposed for the determination of the trace amounts of iron, nickel, and tin in zircaloys. A zircaloy sample was dissolved in a mixture of tetrafluoroboric acid and hydrochloric acid, diluted to a definite volume with water. After the addition of 3 cm3 of 1% (R,R)-tartaric acid solution as an auxiliary chelating agent and 50 μg of cobalt as an internal standard to an aliquot (less than 200 μg of tin) of the solution, the pH was adjusted to 2 with ammonia solution and 3 cm3 of 1% hexamethyleneammonium hexamethylenedithiocarbamate (HMA–HMDC) was added. The resulting HMA–HMDC complexes were collected on a membrane filter and dried. The contents of iron, nickel, and tin in zircaloys were calculated by the calibration curves with the ratios of Kα intensities for each element to that for cobalt. The coefficients of variation (5 results for each metal) were 2.16, 0.63, and 1.52% for 10, 10, and 200 μg of iron, nickel, and tin, respectively. The analytical results of iron, nickel, and tin in zircaloy samples by the proposed method agreed with the certified values.
  • Kisaburo Umemoto, Toyohumi Saeki, Niro Matsuura, Katsue Motegi
    1982 Volume 55 Issue 3 Pages 746-749
    Published: 1982
    Released: June 27, 2006
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    Reaction of hyperoxide with Fe(phen)32+ in DMSO was studied by polarography, cyclic voltammetry, and spectroscopy. Voltammetric study of oxygen showed that disproportionation of hyperoxide is promoted by Fe(phen)32+. Controlled potential coulometry exemplified the stoichiometry of the reaction to be 2:1 for hyperoxide to Fe(phen)32+ in support of the proposed disproportionation mechanism of hyperoxide. Analysis of reaction products proved that Fe(phen)32+ decomposes on reaction with hyperoxide in DMSO; the reaction products were iron(III) hydroxide and liberated ligands, neither metal hyperoxide nor oxygen bridged metal complexes being detected.
  • Mitsuru Sano, Hiroshi Kashiwagi, Hideo Yamatera
    1982 Volume 55 Issue 3 Pages 750-753
    Published: 1982
    Released: June 27, 2006
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    An ab initio MO calculation of [Ni(CN)4]2− has been carried out with a double zeta basis set. The nickel-cyanide interactions are discussed and the electronic change occurring on the coordination of CN to Ni2+ is shown by using the MO contours and the electron-density difference map. The map shows σ donation from the cyanide orbitals and π back-donation from the metal dxy orbital.
  • Yutaka Taniguchi, Yoichi Shimura
    1982 Volume 55 Issue 3 Pages 754-758
    Published: 1982
    Released: June 27, 2006
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    In a thick suspension circular dichroism cannot be directly determined by the Grosjean-Legrand type CD instrument, because Lambert’s law does not hold in it. The transfer of light intensity is discussed when polarized light is incident on a plane-parallel scattering medium containing randomly oriented, optically active particles. This problem is analyzed based on a two-beam radiative transfer model. We provide a method to determine the molar CD in a multiple scattering system. The measurements of ellipticity and transmittance with conventional instruments is served for our method by using a plate of opal glass. The molar CD is determined in Nujol mulls of Λ-[Co(en)3]Br3·H2O and [Co(NH3)6](d-tart)1.5·5H2O. The results are reproducible and reliable.
  • Satoshi Tachiyashiki, Hideo Yamatera
    1982 Volume 55 Issue 3 Pages 759-763
    Published: 1982
    Released: June 27, 2006
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    The rates of racemization and dissociation of [Fe(phen)3]2+ were determined in the presence of series of alkali-metal bromides, symmetrical tetraalkylammonium bromides, and alkyltrimethylammonium bromides. The alkali-metal bromides did not affect the racemization rate, but they decreased the dissociation rate. The retarding effect increased with increasing bromide concentrations and decreased in the order of Li+>Na+>K+> Rb+>Cs+. The alkylammonium bromides increased the racemization rate up to three fold and decreased the dissociation rate down to half the rate in pure water; alkylammonium ions with longer alkylchains induced greater changes of the rates. The effect of alkylammonium ions on the reaction rates was analyzed in terms of the formation of 1:1 aggregates of the complex cation with the alkylammonium cation caused by hydrophobic interactions. The equilibrium constant for the aggregate formation was greater for the alkylammonium ions with longer alkyl chains. The reaction rate constants of the hydrophobic aggregates remain almost constant with the increase in the alkyl chain length. The rate behaviors of the hydrophobic aggregates are discussed in terms of the reaction mechanisms of racemization and dissociation of [Fe(phen)3]2+.
  • Kan Kanamori, Kiyoyasu Kawai
    1982 Volume 55 Issue 3 Pages 764-768
    Published: 1982
    Released: June 27, 2006
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    The Raman and the infrared spectra of tetraamminecobalt(III) complexes have been measured to find the vibrational criteria for differentiating between the cis and trans configurations. Conspicuous differences between the isomers were found in the ν(Co–NH3) region. Thus, generally the trans isomers have two bands at ca. 480 and ca. 450 cm−1 in the Raman spectra and one band at ca. 510 cm−1 in the infrared spectra, and the mutual exclusion rule virtually holds. On the other hand, the cis isomers have more than three bands in the region of both the Raman and the infrared spectra.
  • Satoshi Kaki, Kazuaki Yamanari, Yoichi Shimura
    1982 Volume 55 Issue 3 Pages 769-774
    Published: 1982
    Released: June 27, 2006
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    The binary and ternary solubility phase diagrams of the racemic and optically active complexes [Co(gly)(en)2]X2 were determined in water (X2=SO4, S2O3, (NO3)2, (SCN)2, (CH3CO2)2, (ClO4)2, (CH3CO2)ClO4, and [Sb2(d-tart)2]). Spontaneous resolution was found for the double salt of [Co(gly)(en)2](CH3CO2)ClO4 at 5–50 °C and for [Co(gly)(en)2]SO4 at 39–50 °C; the latter of these has been shown to crystallize as both a racemic compound (below 39 °C) and a conglomerate (above 39 °C).
  • Akira Fuyuhiro, Kazuaki Yamanari, Yoichi Shimura
    1982 Volume 55 Issue 3 Pages 775-779
    Published: 1982
    Released: June 27, 2006
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    A part of quaternary solubility isotherm, (Λ-[Co(en)3]3+, Δ-[Co(en)3]3+, H+)–(R,R)-C4H4O62−–H2O, CH+≤C(R,R)-C4H4O62−, was determined at 25 °C. It was found that three double salts Λ- and Δ[Co(en)3](d-C4H5O6)· (d-C4H4O6nH2O and Λ-[Co(en)3]0.48 ·Δ-[Co(en)3]0.52(d-C4H4O6)1.5·5H2O exist, three invariant points appearing. The yield for optical resolution of [Co(en)3]3+ found to be constant regardless of [H+]. The existence of complete ternary system containing double salts, Λ-[Co(en)3](d-C4H5O6)(d-C4H4O6)–Δ-[Co(en)3](d-C4H5O6)(d-C4H4O6)–H2O, was found and the solubilities of Λ- and Δ-[Co(en)3](d-C4H5O6)(d-C4H4O6) were measured at 5–65 °C.
  • Kiyoshi Sawada, Kazue Miura, Toshio Suzuki
    1982 Volume 55 Issue 3 Pages 780-784
    Published: 1982
    Released: June 27, 2006
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    The equilibria of a series of complexes of the CoBr2(R-py)2 type (where R-py=2-methyl-(2Me-py), 3-methyl-(3Me-py), 4-methyl-(4Me-py), 4-acetyl-(4Ac-py), and 4-cyanopyridine (4CN-py), and pyridine(py)) with TBA·Br (tetrabutylammonium bromide) in 1,2-dibromoethane have been investigated spectrophotometrically. In the presence of an excess of R-py, the dibromocomplex gives rise to the following configurational equilibrium:
    CoBr2(R-py)2+2R-py\oversetkc\ ightleftharpoonsCoBr2(R-py)4
    (tetrahedral)&(octahedral)
    with logKc=0.67, 0.11, and 0.53±0.03 for the 4Me-py, 3Me-py, and py complexes respectively. The substitution equilibria of the tetrahedral complexes are written as:
    CoBr2(R-py)2+TBA·Br\oversetk3\ ightleftharpoons(TBA)CoBr3(R-py)+R-py,
    (TBA)CoBr3(R-py)+TBA·Br\oversetk4\ ightleftharpoons(TBA)2CoBr4+R-py.
    The successive formation constants, logK3, were determined as 2.23, 2.44, and 2.89±0.03 for the 4Me-py, 3Me-py, and py complexes respectively. The constants logK4 for the 4Me-py, 3Me-py, 2Me-py, py, 4Ac-py and 4CN-py complexes are −1.07, −0.94, 0.09, −0.74, −0.09, and 0.47±0.01 respectively. The values of logK3 and logK4 show a linear correlation with the basicity of R-py, pKb, except for the 2Me-py complex.
  • Kenichi Okazaki, Kazuo Saito
    1982 Volume 55 Issue 3 Pages 785-791
    Published: 1982
    Released: June 27, 2006
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    New optically active vanadium(IV) and (V) and mixed valence(IV,V) complexes containing a quadridentate ligand (S)-N-[1-(2-pyridyl)ethyl]iminodiacetate (S-peida2−) have been prepared: i.e. uninuclear distorted octahedral [VIVO(S-peida)(H2O)] and Li[Vv(O)2(S-peida)], a mixed valence binuclear Na[V2IV,VO3(S-peida)2], and an oxo-peroxo complex Na[VvO(O2(2−))(S-peida)]. The tertiary amino nitrogen of S-peida2− occupies the trans position to the oxo ligand in the first three complexes, but trans to the peroxo ligand in the last complex. Three absorption bands of [VIVO(S-peida)(H2O)] in the region from 10000 to 30000 cm−1 have been assigned to the d-d transitions, dxy→(dxz,dyz), dxy→dz2−y2, and dxy→dz2, in the order of increasing frequency. The mixed valence complex gives an intervalence transfer band and two d-d bands in the region from 9000 to 25000 cm−1. It gives a negative and a positive CD peak corresponding to the intervalence transition. The VV(O)2 and the VVO(O2) complex give a characteristic absorption shoulder at 25000 and a peak at 23500 cm−1 with corresponding weak negative CD peaks, respectively. They are assigned to charge transfer bands from oxo and peroxo to VV, respectively. The sign of CD peaks seems to be governed mostly by asymmetric arrangement of the ligating atoms and asymmetric deviation of ligating atoms from regular octahedron.
  • Yasushi Inoue, Yoshimune Yamada
    1982 Volume 55 Issue 3 Pages 792-796
    Published: 1982
    Released: June 27, 2006
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    The phase transformation of Na2Zr(PO4)2·3H2O which had been obtained from zirconium(IV) bis(hydrogenphosphate) monohydrate(α-zirconium phosphate), prepared by the direct precipitation method, was studied by means of gravimetry, X-ray analysis, and acid-base titration. When the material was heated for 2 d, it was transformed to a monohydrate at 80 °C and then successively to three anhydrous phases, depending on the temperature. The monohydrate was also formed by letting the trihydrate stand over P2O5 at room temperature for longer than two weeks. The processes were confirmed to be irreversible by an examination of the rehydration behavior, from which the conditions of the storage of five modifications of disodium zirconium(IV) bis(orthophosphate) were established. It is of special interest that the second anhydrous phase reverted to the first one when it was allowed to stand at room temperature in air or in a desiccator. The rate of the reversion decreased with the temperature of heat-treatment and with a decrease in the relative humidity of the surroundings. The difference between the present results and Clearfield’s was clarified and attributed mainly to the difference in the crystallinity of the starting α-zirconium phosphate.
  • Masato Ikeda, Kunio Shimizu, Gen P. Satô
    1982 Volume 55 Issue 3 Pages 797-801
    Published: 1982
    Released: June 27, 2006
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    An oxo-bridged, mixed-valence complex of ruthenium(IV,III), [(edta)RuIVORuIII(edta)3−, has been obtained from the oxidation of [RuIII(edta)(H2O)] by chlorate ions. The formulation of the complex as a μ-oxo dimer of ruthenium(IV,III) is based on the results of a variety of experiments, including elemental analyses, magnetism, by spectrophotometry, and by electrochemical studies. These studies in acetate buffer solution show that the dimeric ion can be reduced at mercury electrode to [(edta)RuIIIORuIII(edta)]4− and then is monomerized to the original [Ru(edta)(H2O)] in a fast reaction.
  • Takeo Adachi
    1982 Volume 55 Issue 3 Pages 802-808
    Published: 1982
    Released: June 27, 2006
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    Using hydrofluoric–boric acid media, a new cation exchange method for the mutual separation of metals which form stable fluoride complexes has been developed. The addition of boric acid to a hydrofluoric acid solution reduces the free fluoride ion concentration to about one hundredth because of the formation of fluoroboric acid. This reduction of the free fluoride ion concentration makes it easy to control the formation of metal fluoride complexes, favoring their separation. As the fluoroboric acid has a buffer action relating to the fluoride ion concentration, the distribution coefficients of metal ions are not affected by the increase in the concentrations of metal ions, even at a low concentration of fluoride ions in the solution. By the use of hydrofluoric–boric acid media, such metals as zirconium, titanium, aluminium, and uranium can be separated from each other. The distribution coefficients of eighteen metals were investigated both in hydrofluoric acid and hydrofluoric–boric acid solutions.
  • Michio Nakashima, Sigeo Kida
    1982 Volume 55 Issue 3 Pages 809-812
    Published: 1982
    Released: June 27, 2006
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    Complete ligand replacement of tris(ethylenediamine)cobalt(III)([Co(en)3]3+) by bis(2-hydroxyethyl)dithiocarbamate ion(htc) forming [Co(htc)3] is induced by visible light in aqueous solution. The quantum yield of the reaction depends on the wavelength of the light and on the concentrations of the complex and the ligand. The distinct feature of this photo-induced substitution is that the quantum yield is higher than unity for the solution containing 0.02 mol dm−3 [Co(en)3]3+ and 0.13 mol dm−3 htc. The unusually high quantum yield is explained on the basis of a primary photoredox process followed by a chain reaction involving cobalt(II) species as chain carriers. Cobalt(III) complexes of an N6 donor set such as [Co(NH3)6]3+, [Co(NH3)4(pn)]3+, [Co(chxn)3]3+, and [Co(dien)3]3+ also undergo similar photo-reaction, where pn, chxn, and dien denote 1,2-propanediamine, 1,2-cyclohexanediamine, and diethylenetriamine, respectively.
  • Kiyoshi Tamura, Shoji Harada, Yoshinori Funaki, Tatsuya Yasunaga
    1982 Volume 55 Issue 3 Pages 813-816
    Published: 1982
    Released: June 27, 2006
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    Temperature-jump relaxation studies have been carried out on aqueous nickel(II)–L-glutamic acid solutions. The observed relaxation phenomenon is ascribed to the successive complex formation reactions:
    Ni2++L2− \oversetk1\undersetk-1\ ightleftharpoons NiL,
    NiL+L2− \oversetk2\undersetk-2\ ightleftharpoons NiL22−,
    NiL22−+L2− \oversetk3\undersetk-3\ ightleftharpoons NiL34−,
    where L2− denotes a glutamate ion. The rate constants are: 2.0×104, 1.1×104, and 9.2×103 M−1 s−1 (1 M=1 mol dm−3) for k1, k2, and k3, and 0.048, 0.69, and 27 s−1 for k−1, k−2, and k−3, respectively, at 25 °C and I=0.1. The rate-determining step of the complex formation reactions, which follows the initial formation of ion-pairs, is the dissociation of a water molecule from the inner hydration sphere of the nickel; the glutamate ion acts as a bidentate ligand forming a five-membered chelate ring in the complexes.
  • Hisanobu Wakita, Mitsuyoshi Ichihashi, Takeharu Mibuchi, Isao Masuda
    1982 Volume 55 Issue 3 Pages 817-821
    Published: 1982
    Released: June 27, 2006
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    An X-ray diffraction analysis of the aqueous nickel(II) bromide solutions with the concentrations of 2.004, 4.064, and 4.845 mol dm−3 demonstrated the presence of the complex [NiBr(H2O)5]+. This inner-sphere type complex has interatomic distances of 2.52–2.58 Å for Ni–Br and of 2.04–2.05 Å for Ni–OH2. With an increase in the concentration the average number of the Ni–Br contacts per one Ni2+ ion increased; it was found to be 0.18, 0.47, and 0.68 in the 2.004, 4.064, and 4.845 mol dm−3 solutions, respectively.
  • Hiroshi Sugimoto, Teruaki Higashi, Masayasu Mori, Motoi Nagano, Zen-ic ...
    1982 Volume 55 Issue 3 Pages 822-828
    Published: 1982
    Released: June 27, 2006
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    μ-Oxo-bis[(hydroxo)(octaethylporphyrinato)ruthenium(IV)] was prepared by the oxidation of (carbonyl)(octaethylporphyrinato)ruthenium(II) with t-butyl hydroperoxide in good yield. Facile replacement of the hydroxyl group with various anions afforded μ-oxo dimer complexes formulated as [{RuIV(oep)X}2O] (X=Cl, Br, and OCOCH3). The same type of osmium complexes, [{OsIV(oep)(OCH3)}O], {[OsIV(oep)(OCH3)}O{OsIV(oep)(OH)}], and [{OsIV(oep)(OH)}2O] were obtained from the air oxidation product of (carbonyl)(methanol)(octaethylporphyrinato)osmium(II) in the presence of 2,3-dimethylindole. These complexes are diamagnetic. The 1H NMR data are in conformity with the linear oxo-bridged dimer structure which was proved by X-ray crystallography with [{RuIV(oep)(OH)}2O]. The redox potentials were measured by the cyclic voltammetry. These complexes showed three distinct quasi-reversible redox couples assignable to metalII/ metalIII, metalIII/metalIV, and porphyrin ligand oxidation, respectively. Significantly lower redox values and anomalous spectral features indicate a strong pπ-dπ interaction between the bridging oxygen atom and the two quadrivalent metal ions.
  • Makoto Ando, Yoji Tachibana, Hiroyoshi Kuzuhara
    1982 Volume 55 Issue 3 Pages 829-832
    Published: 1982
    Released: June 27, 2006
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    Racemic 15-formyl-14-hydroxy-5,5-dimethyl-2,8-dithia[9](2,5)pyridinophane (4), an analog of pyridoxal having a branched “ansa chain” between 2′- and 5′-positions, was synthesized from 2,5-bis(chloromethyl)-3-hydroxy-O,O′-isopropylidene-4-pyridinemethanol. Optical resolution of 4 was achieved via the formation of Schiff base with 3-amino-3-deoxy-1,2:5,6-di-O-isopropylidene-D-glucofranose, giving the levorotary enantiomer of 4 (4a). Racemic 15-aminomethyl-14-hydroxy-5,5-dimethyl-2,8-dithia[9](2,5)pyridinophane (5), the same type of pyridoxamine analog as 4, and its levorotary enantiomer were synthesized from the corresponding 4 and 4a. Both levorotary and dextrorotary enantiomers of 5 were also obtained by the optical resolution of the racemate via the formation of chiral dibenzoyltartaric acid salts of 5.
  • Shoji Kajigaeshi, Shizuo Fujisaki, Yasuhiko Nakashige, Sadaaki Murakam ...
    1982 Volume 55 Issue 3 Pages 833-837
    Published: 1982
    Released: June 27, 2006
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    The kinetics and mechanism of reduction of 9,9′-bifluorenylidene (1) by sodium isopropoxide (2) in isopropyl alcohol to yield 9,9′-bifluorenyl (3) were investigated spectrophotometrically. The kinetic data suggest that the reduction proceeds autocatalytically, the reduction product 3 acting as the catalyst. It was found that
    1\xrightarrow[2]k13 (1) 1+3\xrightarrow[2]k23+3 (2)
    Reactions 1 and 2 are of the first order with respect to 1, but that the former is of the third order with respect to 2, whereas the latter is of the first. The fourth- and third-order rate constants, k1 and k2, for Reactions 1 and 2 were determined to be 3.0×10−5 dm9 mol−3 s−1 and 1.1×103 dm6 mol−2 s−1, respectively, at 130 °C. Probable mechanisms for Reactions 1 and 2 have been offered on the basis of the reaction order for each molecular species involved.
  • Kenichiro Arai, Yoshitaka Ogiwara
    1982 Volume 55 Issue 3 Pages 838-841
    Published: 1982
    Released: June 27, 2006
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    The secondary solubilization of dextrin in a dodecylbenzenesulfonic acid (DBSH) reversed micelle in benzene containing a small amount of water was examined; a perfectly clear solution was obtained. The solution showed a CMC of DBSH, estimated by the method of Methylene Blue methachromasis, just like that of sucrose-containing similar reversed-micelle system. The hydrolysis of the dextrin in the system was investigated; the maximum rate enhancement of 285-fold was obtained on the basis of the reaction in DBSH aqueous solution. The CMC and the reaction rate showed changes similar to those in the case of sucrose-containing similar reversed-micelle system with changing the amount of water solubilized, but they showed different changes with changing the concentration of the substrate. These different changes were supposed to result from the differences in the molecular weights of the substrates. These results suggested that the rate enhancement mechanism due to solvent effect and micelle effect which was proposed for the hydrolysis of sucrose in the presence of a DBSH reversed micelle operates in the hydrolysis of the high molecular weight substrate such as dextrin.
  • Nobutaka Suzuki, Kaniti Sano, Satoshi Wakatsuki, Yasuji Izawa
    1982 Volume 55 Issue 3 Pages 842-844
    Published: 1982
    Released: June 27, 2006
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    Photosensitized oxygenation of (benzylidenehydrazono)-, (diphenylmethylenehydrazono)-, (9-fluorenylidenehydrazono)-, (9-xanthenylidenehydrazono)-, and (10-methyl-9,10-dihydroacridin-9-ylidenehydrazono)triphenylphosphoranes at −78 °C gave the corresponding carbonyl compounds and triphenylphosphine oxide and also gave light emission upon warming-up to room temperature.
  • Eiichi Ibuki, Shigeru Ozasa, Yasuhiro Fujioka, Hiroshi Mizutani
    1982 Volume 55 Issue 3 Pages 845-851
    Published: 1982
    Released: June 27, 2006
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    Six new 1,8-diarylnaphthalenes, each having closely held parallel aromatic rings, were synthesized by a Kharash-type Grignard cross-coupling of arylmagnesium iodide and 1,8-diiodonaphthalene in the presence of N,N′-bis(1-methyl-3-oxobutylidene)ethylenediaminatonickel(II) as a catalyst. Among them, 1,8-di(1-naphthyl) naphthalene was obtained as cis and trans rotamers, caused by the restricted rotation at the 1,8-position. Interconversion between the rotamers on heating above their melting points was confirmed by differential scanning calorimetry. The proton magnetic resonance spectral studies of the 1,8-diarylnaphthalenes indicated the presence of a face-to-face arrangement of aromatic rings in the peri-position. Two new 8,8′-diaryl-1,1′-binaphthyls, each having two sets of closely held parallel aromatic rings, were isolated as minor coupling products. Trans-trans conformations were proposed for them on the basis of their thermal behavior. Several nickel(II) complexes were found to be effective catalysts for preparative Grignard cross-coupling reaction involving closely crowded geometry.
  • Hidemasa Takaya, Masashi Yamakawa, Ryoji Noyori
    1982 Volume 55 Issue 3 Pages 852-858
    Published: 1982
    Released: June 27, 2006
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    In the presence of bis(acrylonitrile)nickel(0) or bis(1,5-cyclooctadiene)nickel(0), exo-tricyclo[3.2.1.02,4]oct-6-ene cycloadds to acrylonitrile and methyl acrylate to give anti- and syn-3-cyano-exo,exo-tetracyclo[4.3.1.02,5.07,9]decane or the corresponding methoxycarbonyl derivatives. The cycloaddition with dimethyl maleate proceeds with retention of configuration. Benzonorbornadiene also enters into the 2+2 reaction, while endo-tricyclo[3.2.1.02,4]oct-6-ene, bicyclo[2.2.1]heptene, and 5-methylenebicyclo[2.2.1]heptene are unreactive. Origins of the observed selectivities in the catalyzed reaction are discussed.
  • Suketaka Ito, Yumo Tanaka, Akikazu Kakehi
    1982 Volume 55 Issue 3 Pages 859-864
    Published: 1982
    Released: June 27, 2006
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    3-Aryl-1,2,4-benzotriazines were obtained in good yields by the mercury(II) oxide-oxidation of N-phenylsulfonyl-N″-arylbenzamidrazones prepared from N-(phenylsulfonyl)benzohydrazonoyl chlorides and anilines. From the synthetic viewpoint for benzotriazines, this method may be of high utility on account of the availability of starting materials and higher yields.
  • Sakaaki Horaguchi, Mamoru Hara, Tsuneo Suzuki
    1982 Volume 55 Issue 3 Pages 865-869
    Published: 1982
    Released: June 27, 2006
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    The reaction of (8-oxo-5,6,7,8-tetrahydro-1-naphthyloxy)acetic acids with acetic anhydride and sodium acetate give a mixture of 4,5-dihydro-3H-naphtho[1,8-bc]furans and lactones. The relative yields of 4,5-dihydro-3H-naphtho[1,8-bc]furans and lactones varied according to kinds of substituents on the benzene ring of (8-oxo-5,6,7,8-tetrahydro-1-naphthyloxy)acetic acids. Substituents which make the methylene group approach closer to the carbony carbon atom of (8-oxo-5,6,7,8-tetrahydro-1-naphthyloxy)acetic acids by a steric effect seem to favor the production of 4,5-dihydro-3H-naphtho[1,8-bc]furans. On the other hand, substituents which make the methylene group separate from the carbonyl carbon atom seem to favor the production of lactones. An electron-withdrawing chlorine atom on the benzene ring of (8-oxo-5,6,7,8-tetrahydro-1-naphthyloxy)acetic acids also favors the production of 4,5-dihydro-3H-naphtho[1,8-bc]furans.
  • Masaaki Yoshifuji, Rihei Nagase, Takayuki Kawashima, Naoki Inamoto
    1982 Volume 55 Issue 3 Pages 870-872
    Published: 1982
    Released: June 27, 2006
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    Reactions of α-aryl-N-methylnitrones with phenylphosphonothioic dichloride (1), diphenylphosphinothioic chloride (6), or thiophosphoryl trichloride (7) gave N-methylbenzamide and N-methylthiobenzamide derivatives, and the latter became major in the presence of tertiary amine. α,N-Diarylnitrones (4) reacted with 1 to give 2-arylbenzothiazoles (5) at room temperature in moderate yields. Reaction of 4 with 6 (at room temperature) or 7 (in refluxing THF) gave 5 in a low yield, whereas a similar reaction of 4 with 7 at 0 °C afforded N-benzylidene-2-chloroaniline in a high yield. A mechanism for the formation of 5 has been discussed briefly.
  • Masaaki Yoshifuji, Rihei Nagase, Naoki Inamoto
    1982 Volume 55 Issue 3 Pages 873-876
    Published: 1982
    Released: June 27, 2006
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    Reactions of α,N-diarylnitrones in the presence of O-methyl diphenylphosphinothioate at 150 °C gave 2-arylbenzoxazoles (3) in fairly good yields. Oxidation of N-alkylidene-2-hydroxyanilines with silver oxide afforded 2-alkenyl-, 2-alkyl-, or 2-arylbenzoxazoles (7 and 3) in good yields under mild reaction conditions (at room temperature). A plausible mechanism for formation of 3 and 7 has been discussed briefly.
  • Michikazu Yoshioka, Haruhiko Osawa, Shinji Fukuzawa
    1982 Volume 55 Issue 3 Pages 877-879
    Published: 1982
    Released: June 27, 2006
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    Irradiation of ethyl 3-oxo-2,4-diphenylbutanoate in hexane gave the products formed by recombination of the radicals (Ph–\dotCH2 and/or Ph–\dotCH–CO2Et) resulting from decarbonylation, together with small amounts of 1,2-diphenylethanol and ethyl α-hydroxyphenylacetate, whereas in benzene no 1,2-diphenylethanol was found. Under oxygen an increased amount of ethyl α-hydroxyphenylacetate and no radical recombination products were observed.
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