Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
59 巻 , 7 号
選択された号の論文の56件中1~50を表示しています
  • Masahiro Kohno
    1986 年 59 巻 7 号 p. 2053-2061
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    The reactions of a system composed of chloro(5,10,15,20-tetraphenylporphyrinato)cobalt(III), [CoIIICl(tpp)], and its π cation radical coordinating axially two chloride anions, [CoIII(tpp)]Cl2, with several phenols were investigated by using ESR and optical absorption spectroscopy. The phenols were oxidized to phenoxyl radicals. The phenols investigated were classified into two groups after taking into account the differences in the reaction activities and their redox potentials, the phenols mainly reacting with [CoIII(tpp)]Cl2 and those reacting with both [CoIIICl(tpp)] and [CoIII(tpp)]Cl2. The oxidation reactions of phenols with [CoIII(tpp)]Cl2 were the second-order. A linear relationship between the rate constants of oxidation and the redox potentials of phenols was recognized. Active species in the reactions were determined to be composed of a chlorine radical which originates from axial ligands of [CoIIICl(tpp)] and [CoIII(tpp)]Cl2, and the porphyrin ligand of [CoIII(tpp)]Cl2 itself. A possible mechanism for the oxidation reactions is proposed. Finally, the reaction scheme of cobalt porphyrin, ([CoII(tpp)], [CoIIICl(tpp)], and [CoIII(tpp)]Cl2) with phenols is compared with oxidation reactions of phenols with horseradish peroxidase.
  • Shuichi Hamada, Koji Bando, Yoshiyuki Kudo
    1986 年 59 巻 7 号 p. 2063-2069
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    Hydrous gallium(III) oxide was produced as monodispersed spherical particles by forced hydrolysis in the presence of sulfate ions, though they partially dissolved and recrystallized. The rate of the reaction degree was empirically expressed under the given conditions as dα⁄dt=1.60α2⁄3(1−α)0.874, where α is the reaction degree. Polymeric hydroxo complexes were confirmed to act as precursors of the monodispersed spherical particles, judging from the fractional changes of the monomeric and polymeric species during the hydrolysis. The role of sulfate ions in the formation of hydrous gallium(III) oxide particles was discussed.
  • Noboru Oyama, Kazuhiko Hirabayashi, Takeo Ohsaka
    1986 年 59 巻 7 号 p. 2071-2080
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    The electropolymerization of 1-pyrenamine (PA) in an acetonitrile solution led to the polymeric film formation on electrode surfaces. The chemical, spectroscopic, electrical and electrochemical characterization of the resulting poly(1-pyrenamine) (PPA) films was carried out. The number-average molecular weight of the PPA film, measured by gel permeation chromatography, was 1.8×103, corresponding to the degree of the polymerization of ca. 8. The PPA films were polymer-anion composites which contained ca. 0.3 anions (e.g., BF4) per repeating aromatic unit, which is considered to be composed of three PA molecules. The oxidized form of the PPA film displayed the ESR response. The g factor was 2.0082 and the concentration of radical in the PPA film was determined to be 4.8×1019 eg−1. The conductivities of the PPA films in the dry state at 300 K were in the range 10−11–10−10 S cm−1. The PPA film was electroactive in an aqueous solution as well as in a non-aqueous solution. The cyclic voltammetric responses depended on pH of aqueous solutions and supporting electrolyte in non-aqueous solutions. The thickness(φ) of the PPA film and the surface concentration(Γ) of the electroactive site in the PPA film were proportional to the amount (Q) of the charge passed during the electrolysis (when Q<ca. 120 mC cm−2). The volume concentrations of the electroactive site were 9.7×10−4 and 1.7×10−3 mol cm−3 for the PPA films prepared in the NaClO4 and TBABF4 (tetrabutylammonium tetrafluoroborate) electrolytes, respectively. From the normal pulse voltammetric, potential-step chronoamperometric and potential-step chronocoulometric experiments of the PPA films in a 0.2 M NaClO4 aqueous solution (pH 1.0), the effective apparent diffusion coefficient (Dapp) for the diffusion-like charge transport within the PPA films, and the standard rate constant (k°) and anodic transfer coefficient (αa) of the heterogeneous electron-transfer reaction between the In2O3 electrode and the electroactive site in the PPA film were estimated to be (1.5±0.5)×10−10 cm2 s−1, (1.9±0.4)×10−5 cm s−1 and 0.67±0.03, respectively.
  • Zeyong Zheng, Takashi Yamane, Tamaichi Ashida, Masaya Morita, Natsuki ...
    1986 年 59 巻 7 号 p. 2081-2084
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    The crystal structure of an isomer of Teucrin P1 isolated from Teucrium gnaphalodes has been determined by the X-ray method. Crystal data: orthorhombic, P212121, a=13.849(4), b=15.545(3), c=7.896(2) Å, Z=4. The final R value is 0.048 for 1247 observed reflections with Fo>2σ(Fo). The structure is disordered, and two kinds of components (molecules) with different conformations coexist in the crystal. The major component exists with a probability of 0.74, while the minor one with 0.26. A tetrahydropyran ring in the former takes a boat form, while the latter a chair form, indicating that in this complex fused-ring system a boat form of the tetrahydropyran ring is more stable than a chair one. The conformation of the major component is the same as that of naturally occurring Teucrin P1, apart from the orientation of a furan ring.
  • Yuanxin Gu, Takashi Yamane, Tamaichi Ashida, Kazuhiko Hashimoto, Hiros ...
    1986 年 59 巻 7 号 p. 2085-2088
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    The crystal structures of the bicyclic oxalactam, 8-oxa-6-azabicyclo[3.2.1]octan-7-one(BOL) and the 4(e)-bromo-substituted derivative(Br–BOL) were determined by the X-ray diffraction method. Crystal data: (BOL) P212121, a=10.926(3), b=9.115(2), c=6.280(2), Å, Z=4; (Br–BOL) P212121, a=10.708(3), b=11.053(3), c=6.208(2), Å, Z=4. Refinements were carried out by the full-matrix least-squares method. R values are; (BOL) 0.050 for 601 reflections, (Br–BOL) 0.028 for 866 reflections. Both structures are quite similar to each other. The packing scheme of BOL is essentially the same as that of Br–BOL. Molecules are linked by N–H···O hydrogen bonds around a two-fold screw axis, giving rise to infinite chains extended along the c axis.
  • Masaharu Ohba, Kiyoshi Arakawa
    1986 年 59 巻 7 号 p. 2089-2092
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    A critical behavior of fluids composed of polar diatomic molecules is studied by the use of the Ornstein–Zernike (OZ) theory of critical phenomena extended to the interaction site model. Firstly, the asymptotic forms of the atom–atom direct correlation functions cαγ(r) for the polar fluids at large separation are obtained, which are valid off the critical point. Then, the OZ hypothesis that the asymptotic forms of cαγ(r) do not change near and at the critical point is examined, and the critical behavior of the total correlation function is investigated. It is found to be completely analogous to the case of simple fluids. The relation between the OZ hypothesis and some integral equation theories is also discussed.
  • Hazime Saitô, Ryoko Tabeta, Takuma Sasaki, Yûko Yoshioka
    1986 年 59 巻 7 号 p. 2093-2101
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    High-resolution solid-state 13C NMR spectra of a variety of (1→3)-β-D-glucans in the solid state were recorded by means of cross polarization-magic angle spinning (CP–MAS) NMR spectroscopy. We found that the C-1 and C-3 peak-positions of these glucans are significantly displaced (up to 8 ppm) depending upon variety of samples used. Interestingly, these glucans obtained by lyophilization or spray-drying possess regular secondary structures as detected by displacements of the conformation-dependent 13C chemical shifts. In fact, at least four kinds of molecular conformations were distinguishable by 13C NMR spectroscopy. Gel-forming ability of linear (1→3)-β-D-glucans, however, was related to the presence of a single particular conformation without involving any other form. By contrast, gel-formation was noted for a branched glucan whose conformation is similar to that of a linear glucan without gel-forming ability. Further, conformation of all these linear and branched (1→3)-β-D-glucans turned out to be the same when solid samples were prepared by lyophilization from DMSO solution.
  • Masanobu Watanabe, Izumi Motoyama, Hirotoshi Sano
    1986 年 59 巻 7 号 p. 2103-2107
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    Biferrocene and ferrocenylruthenocene react with HgCl2 to give very stable adducts. Large quadrupole splitting values (2.93 mm s−1 for biferrocene–2HgCl2 and 2.99 mm s−1 for ferrocenylruthenocene–5HgCl2, both at 78 K) indicate the presence of a direct interaction between the Fe and Hg atoms. The stabilities of their adducts suggest a chelating effect between the Fe and Fe or Fe and Ru atoms in biferrocene or ferrocenylruthenocene, respectively.
  • Masanobu Watanabe, Izumi Motoyama, Hirotoshi Sano
    1986 年 59 巻 7 号 p. 2109-2113
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    Adducts of tin(IV) halide with [2]ferrocenophane were prepared by treating SnX4 (X=Cl or Br) with [2]ferrocenophane in hexane. The adducts were studied by means of 57Fe- and 119Sn-Mössbauer spectroscopy and other physicochemical measurements. Anomalously large quadrupole splittings (3.49 mm s−1 for [2]ferrocenophane–1.5SnCl4 adduct and 3.47 mm s−1 for [2]ferrocenophane–1.5SnBr4 adduct, both at 78 K) found in the 57Fe-Mössbauer spectroscopy and organotin(IV) species (e.g., isomer shift value, 2.14 mm s−1 for the [2]ferrocenophane–1.5SnCl4 adduct and 2.10 mm s−1 for the [2]ferrocenophane–1.5SnBr4 adduct, both at 78 K) found from the 119Sn-Mössbauer spectroscopy suggest that a direct chemical bonding between Fe and Sn atoms is formed in the [2]ferrocenophane adducts, as the Ru–Sn bonding in the ruthenocene–1.5SnCl4 adduct (isomer shift value, 2.08 mm s−1 at 78 K).
    (Remark: Graphics omitted.)
  • Takashi Imai, Masao Nakamura, Kiyofumi Nagai, Yoshiyuki Ohki, Yasuo Su ...
    1986 年 59 巻 7 号 p. 2115-2122
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    Two types of the mixed complexes indicated in the title have been synthesized, and their crystal and molecular structures of the lanthanum (1) and the europium (2) complexes have been determined by the X-ray diffraction method. Both 1 and 2 are monoclinic, space group P21n, and Z=4. 1, a=17.354(7), b=23.336(4), c=10.955(2) Å, β=96.04(2)°, final R value calculated from 4870 reflections is 0.069; 2, a=29.846(7), b=20.070(3), c=14.057(3) Å, β=92.13(2)°, final R value calculated from 7811 reflections is 0.077. In 1, the central metal atom is octa-coordinated, and is in a dodecahedral geometry, where all O,O′-diisopropyl dithiophosphato ligands (iPr2dtp) span m-edges of the dodecahedron, chelating through both of the respective sulfur atoms. Dimethyl sulfoxide (dmso) ligands occupy the apexes of the other m-edge. In 2, the europium(III) metal atom of the cationic species is hepta-coordinated and is in a pentagonal-bipyramidal geometry where two oxygen atoms of dmso ligate from respective ends of the axis and one oxygen atom of the remaining dmso from the equatorial direction. The central metal atom of the anion is octa-coordinated and is in a dodecahedron; where all m-edges are spanned by iPr2dtp ligands. The solid and the acetonitrile solution of 2 is orange in color due to the charge-transfer band (λmax=415 nm; εmax=1.5×102 dm3 mol(Eu)−1 cm−1).
  • Yuzo Yoshikawa, Nobuyuki Kato, Yuito Kimura, Shunji Utsuno, Gopal N. N ...
    1986 年 59 巻 7 号 p. 2123-2128
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    The preparation, separation, and characterization of isomeric complexes of type [CoN6]3+, containing one, two, or three molecules of NH3, en, dien, trien, and tetren (n=0, 1, 2, 3, and 4, respectively for H2N(CH2CH2NH)nH) are reported. All the possible five stereoisomers for [Co(NH3)(en)(dien)]3+ and six stereoisomers for [Co(en)(trien)]3+ have been successfully isolated, but only three of four possible geometrical isomers could be obtained for [Co(NH3)(tetren)]3+. These were characterized by electronic, circular dichroism (CD), and 13C{1H} NMR spectroscopy. Conformational analyses were, also, carried out and the stability, or formation of each isomer at the equilibrium state, is discussed from the calculated strain-energy data and experimental formation ratios.
  • Toshie Harazono, Hiroshi Fukutomi
    1986 年 59 巻 7 号 p. 2129-2133
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    Paramagnetic shifts of DMF (N,N-dimethylformamide) and DMA (N,N-dimethylacetamide) induced by U(V) were studied by the 1H and 13C NMR spectroscopy. It was found that the 1H and 13C NMR signals of bulk DMF and DMA exhibited the paramagnetic shifts to the higher field by U(V). Positive pseudocontact shift and negative contact shift for both DMF and DMA are discussed on the basis of the electronic structure of U(V) complexes. The values of magnetic susceptibilities of U(V) complexes are also presented.
  • Yasuki Yoshimura, Nobuyoshi Sato, Makoto Kikuchi
    1986 年 59 巻 7 号 p. 2135-2140
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    The solubility (Xs) of tris(2,4-pentanedionato)cobalt(III) ([Co(acac)3]) in mixed solvents of water and dimethyl sulfoxide (DMSO) with various compositions was determined over the temperature range 20–60 °C. It was found that the experimental values of Xs could be satisfactorily fitted to lnXs=A(1⁄T)+BlnT+C and the partial molar enthalpy of solution (Δ\barHs) at 25 °C for [Co(acac)3] was estimated from slopes of the solubility curves. When Δ\barHs was plotted against the mole fraction of DMSO (XDMSO), a clear maximum was found at about XDMSO=0.3. This composition profile of Δ\barHs is discussed in connection with the internal pressure of a mixture of water and DMSO. A method to estimate an approximate value of the partial molar enthalpy of hydrophobic hydration (Δ\barHh) in an aqueous DMSO mixture of [Co(acac)3] is also presented by using the solubility data in mixtures with a lower XDMSO than 0.14.
  • Kiyoshi Isobe, Kazuharu Nanjo, Yukio Nakamura, Shinichi Kawaguchi
    1986 年 59 巻 7 号 p. 2141-2149
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    Oxidative addition reactions of 2-chloropyridine, 2,6-dichloropyridine, 2-chloropyrazine, and 2-chlorobenzothiazole with tetrakis(triphenylphosphine)palladium(0) gave [{PdCl(R)(PPh3)}2] or trans-[PdCl(R)(PPh3)2] depending on the nature of the carbon-bonded heterocycles R. They are all stable and the chloride ligand is readily replaced by other halides and pseudohalides. These novel organopalladium(II) complexes were characterized by the analytical and molecular-weight data together with IR, 1H NMR and 13C NMR spectra, and the 2-pyridyl-bridged dinuclear structure of [{PdBr(C5H4N-C2)(PPh3)}2] was previously revealed by X-ray analysis. Both of the dinuclear and mononuclear 6-chloro-2-pyridylpalladium(II) complexes catalyze the cross coupling reaction between 2,6-dichloropyridine and methylmagnesium bromide to afford 2-methyl-6-chloropyridine selectively. The mononuclear 6-chloro-2-pyridylpalladium(II) complexes react with carbon monoxide to form the acyl complexes.
  • Nobuko Matsuoka
    1986 年 59 巻 7 号 p. 2151-2155
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    The MCD spectra of seventeen cobalt(III) complexes were measured in the visible and near-ultraviolet regions. Their behavior in the second d–d absorption band region were compared with those of the [Co(ox)x(gly)y(en)z] series comprising sixteen complexes (x, y, z=0, 1, 2, 3; and x+y+z=3), in which a positive band had been observed on the lower-energy side of the main negative band in this region. For the present work, the positive band was found in [Co(tn)3]3+, cis-[Co(ox)2(NH3)2], cis-[Co(OH2)2(en)2]+, trans-[Co(β-ala)2(en)]+, mer- and fac-[Co(picol)3] (picol=picolinate(1–)), and [Co(acac)3]. It is pointed out that all the complexes exhibiting a positive band were the tris(chelate) or cis-bis(chelate) types. Therefore the origin of this band is discussed in terms of the arrangement of two or three chelate rings. A positive band was not observed for complexes containing a CO32− ligand, even if they were a tris(chelate) or cis-bis(chelate) type. This is explained from a structural basis. The two complexes which had a split second d–d absorption band, mer-trans(NH3)-[CoCO3(gly)(NH3)2] and [CoCO3(picol)(NH3)2], showed two negative bands in the corresponding regions to both component absorption bands, in each complex.
  • Minoru Sakurai, Satoshi Tomomasa, Yûji Seiya, Yoshio Inoue, Riic ...
    1986 年 59 巻 7 号 p. 2157-2164
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    Nε-Retinylidenelysyl peptides containing Tyr and Phe were prepared in order to investigate the effect of the surrounding microenvironment on the absorption maximum of the chromophore of bacteriorhodopsin. The absorption maximum of the retinylidene Schiff base of the lysyl peptide, Boc–Lys–Phe(or –Gly)–Tyr–OMe, was shifted to the red relative to the peptides lacking Tyr, Boc–Lys–Phe–Phe–OMe and Boc–Lys–Phe–OMe. UV and 13C NMR studies on the Tyr-containing lysyl-peptide have confirmed an intramolecular interaction between Tyr and the retinylidene portion in low dielectric media. A hydrogen-bond formation of the Schiff base with a Tyr side chain is supported by a theoretical estimation of the transition energy and the shielding constants for some models of Tyr-Schiff base complexes. The side-chain conformation of the Tyr-contaning lysyl-peptide is discussed in terms of the 1H NMR data. The hydrogen-bonding shift induced by Tyr was estimated as being no less than 10 nm.
  • Chino Yijima, Toshio Tsujimoto, Kohji Suda, Masashige Yamauchi
    1986 年 59 巻 7 号 p. 2165-2170
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    Substituent effects on the 13C and 1H NMR chemical shifts of the α-position of various α-(p-substituted phenyl)nitrones, α-phenyl-N-(1-cyano-2-methylpropyl)nitrones (1), α-phenyl-N-methylnitrones (2), and α-phenyl-N-phenylnitrones (3), have been investigated and the obtained results have been compared with data related to N-(p-substituted benzylidene)anilines (4) and reported data for p-substituted styrenes (5). The chemical shifts of the α-arylnitrones are well correlated with substituent constants by means of a linear combination of two empirical parameters, σi and σπ. Inductive effects predominate at the α-carbon but resonance effects predominate at the α-hydrogen.
  • Shin-ichi Ogata, Amane Mochizuki, Masa-aki Kakimoto, Yoshio Imai
    1986 年 59 巻 7 号 p. 2171-2177
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    The reaction between amines and carboxylic aicds in the presence of polyphosphoric acid trimethylsilyl ester (PPSE) has been investigated from the view point of the synthesis of amides and amidines. Benzanilide was selectively prepared from benzoic acid and aniline in the presence of PPSE and pyridine at 100 °C, whereas a mixture of benzanilide and N,N′-diphenylbenzamidine was obtained without the use of pyridine. The reaction at 160 °C almost exclusively gave N,N′-diphenylbenzamidine. Various symmetrical amidines were obtained from combinations of carboxylic acids and aromatic amines in high yields by simply heating at 160 °C with four molar amounts of PPSE. The reactions of aliphatic and aromatic amines with N-monosubstituted and N,N-disubstituted amides also afforded corresponding unsymmetrical amidines under the same conditions. The reaction mechanism is discussed in some detail.
  • Nobumasa Kamigata, Hirokazu Iizuka, Akira Izuoka, Michio Kobayashi
    1986 年 59 巻 7 号 p. 2179-2183
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    The photochemical reaction of 2-aryl-1,2-benzisoselenazol-3(2H)-ones (1) in benzene was found to give dibenzo[b,f][1,4]selenazepin-11(10H)-ones (2). On the other hand, the photochemical reaction of 1 in t-butyl alcohol afforded 2-(2-hydroxy-2-methylpropylseleno)benzanilide, 2-(methylseleno)benzanilide, and 2-aryl-1,2-benzisoselenazol-3(2H)-one 1-oxides together with the photoisomer 2. Mechanisms for these reactions are proposed.
  • Kaoru Inami, Tetsuo Shiba
    1986 年 59 巻 7 号 p. 2185-2189
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    Four analogs of an antibiotic althiomycin were synthesized in order to clarify the structure-activity relationships, especially with regard to two asymmetric centers and the aldoxime configuration. The antibiotic activity of de(hydroxymethyl) analog is comparable to that of the original antibiotic for Gram-positive bacteria.
  • Takahiro Hosokawa, Takanori Kono, Toru Uno, Shun-Ichi Murahashi
    1986 年 59 巻 7 号 p. 2191-2193
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    Reaction of 2,3-dihydro-2-vinylbenzofuran with nucleophiles (NaCH(COOEt)2 and PhNHCH3) in the presence of palladium catalysts such as Pd(PPh3)4 and PdCl2(PR3)2 (R=Ph and Et) gives 2-(2-butenyl)phenols (46–76% yields) in which nucleophiles are incorporated into the methyl group of the butenyl moiety. 2-Vinylchroman undergoes the same type of reaction where only the palladium complex bearing PEt3 ligand is effective. The effectiveness of PEt3 ligand is also observed in the reaction of 2,3-dihydro-2-isopropenylbenzofuran with diethyl sodiomalonate leading to 3-ethoxycarbonyl-4-(2-methyl-1-propenyl)-2-chromanone.
  • Syun Egusa, Jun Takagi, Masahiko Sisido, Yukio Imanishi
    1986 年 59 巻 7 号 p. 2195-2201
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    Cyclic dipeptides of aromatic amino acids, cyclo(L-phenylalanyl)2, cyclo(L-1-naphthylalanyl)2, and cyclo(L-2-naphthylalanyl)2 were synthesized and subjected to spectroscopic analyses using 1H NMR, absorption, circular dichroism (CD), fluorescence, and fluorescence-detected circular dichroism (FDCD). The 1H NMR data suggested that the 2,5-piperazinedione rings of the three cyclic dipeptides are in planar or nearly planar bowsplit boat-type conformation. The aromatic side groups of cyclo(1- and 2-naphthylalanyl)2’s were found to take asymmetric configurations, one naphthyl group being folded onto the 2,5-piperazinedione ring, the other being unfolded. Strong exciton couplet was observed in CD spectra of the three compounds. The signs of the exciton splitting were opposite in the two naphthyl cyclic dipeptides. Fluorescence spectra of the two naphthyl cyclic dipeptides showed no excimer emission. The absence of strong interchromophoric interaction in the lowest excited state was also suggested by the virtual coincidence of CD spectrum with FDCD spectrum. From the above spectroscopic data, probable conformations were proposed for the naphthyl cyclic dipeptides.
  • Kaoru Harada, Shinnichiro Suzuki, Hideyuki Narita, Hiroshi Watanabe
    1986 年 59 巻 7 号 p. 2203-2207
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    (N-Salicylideneglycyl-L-valinato)copper(II) or (N-salicylideneglycyl-L-isoleucinato)copper(II) was treated with formaldehyde in an aqueous solution under relatively mild conditions. It was found that the resulting seryl residue was D-configuration in the early stage of the reaction. However, the configuration was inverted from D- to L-form after prolonged reaction. The epimerization reactions of authentic (N-salicylideneglycyl-D- or L-seryl-L-isoleucinato)copper(II) were carried out under similar conditions. These results indicate that the reaction as a whole is controlled kinetically as well as thermodynamically.
  • J\={u}ro Ojima, Koji Yamamoto, Tadahito Kato, Kazuyo Wada, Yoshiharu Y ...
    1986 年 59 巻 7 号 p. 2209-2215
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    Bisdehydrodibenzo[14]-, -[16]-, -[18]-, -[20]-, and -[22]annulene were synthesized by intramolecular reductive couplings using a low-valent titanium reagent. These bisdehydrodibenzo-annulenes proved to be atropic from an examination of the 1H NMR spectra.
  • Hidefumi Hirai, Keiichiro Wada, Makoto Komiyama
    1986 年 59 巻 7 号 p. 2217-2223
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    An active carbon-supported copper(I) chloride (CuCl) is prepared by stirring active carbon in aqueous hydrochloric acid solution of CuCl, followed by removal of the liquid phase under 6 mmHg at 100 °C. The resulting solid rapidly adsorbs carbon monoxide (CO) at 20 °C from 9:1 CO–N2 mixture under 1 atm (the CO partial pressure 0.9 atm) and the equilibrium molar ratio of adsorbed CO to CuCl is 0.88. All of adsorbed CO is promptly desorbed either by reducing CO partial pressure to 0.4 mmHg at 20 °C or by elevating temperature from 20 °C to 120 °C under 1 atm (the CO partial pressure 0.9 atm). Reversible adsorption-desorption cycles are repeated four times without measurable decrease in the adsorbing capacity. The adsorbing capacity of the active carbon-supported CuCl is much larger than either that of CuCl solid or that of active carbon. Effective CO adsorption by the present adsorbent is attributed to formation of complex between CO and CuCl, which is highly dispersed on the surface of active carbon.
  • Kunihiko Takeda, Minoru Akiyama, Fumiaki Kawakami, Mitsunaga Sasaki
    1986 年 59 巻 7 号 p. 2225-2232
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    The chromatographic separation of rare earth elements was studied using newly-synthesized chelating resins which have EDTA (ethylenediaminetetraacetic acid) and DTTA (diethylenetriaminetetraacetic acid) pendant groups. The chromatography using EDTA- and DTTA-chelating resins gave excellent separation results, while the IDA-chelating resin was not satisfactory. The DTTA-type resin was especially effective, allowing highly purified rare earth elements to be recovered. The separation efficiency of each resin was attributed mainly to the difference in its complexing capability among rare earth ions. Prior to experimentation, the chromatographic conditions were assessed and optimized by computer simulation based on newly introduced equations. The simulation results were effective in the case of Pr3+/Nd3+ for determining the experimental conditions. An analysis of the experimental results helped to elucidate the mechanism of the chromatographic separation while using the simulation results.
  • Isao Oonishi, Shoji Fujisawa, Junji Aoki, Yuji Ohashi, Yoshio Sasada
    1986 年 59 巻 7 号 p. 2233-2236
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    The title compound, C34H18, has been obtained by reducing violanthrone B, a byproduct in the synthesis of violanthrone. Its structure has been determined by on X-ray analysis. The space group is P21/c, with unit-cell dimensions a=25.78(1), b=3.807(5), c=19.975(8) Å, β=96.55(3)°, and Z=4. The structure was solved by the direct method and refined by a block-diagonal least-squares method to an R value of 0.076 on the basis of 1242 independent reflections. The molecules are largely distorted from a planar structure owing to a steric repulsion between the intramolecular overcrowded hydrogen atoms. Also, they are stacked face-to-face to form a column structure along the b-axis.
  • Chiyoko Nakazato, Takahiro Masuda
    1986 年 59 巻 7 号 p. 2237-2239
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    Relative rates of reaction of electrons produced in gamma-irradiated zeolite (Molecular Sieve 13X) with several electron scavengers were determined by competition kinetics using dinitrogen monoxide as a reference compound. A part of the electrons produced in irradiated zeolite have been disclosed to be quasi-free from the feature of their reactivity toward electron scavengers that the reactivity is similar to that of quasi-free electrons found in irradiated liquid 2,2-dimethylpropane. An analysis based on competition kinetics has provided a value 9.8×1012 dm3 mol−1 s−1 as the lower limit on the rate constant for the reaction of quasi-free electrons with positive holes produced in irradiated zeolite.
  • Shunzo Yamamoto, Yo-ichi Ishikawa, Shigeyoshi Arai
    1986 年 59 巻 7 号 p. 2241-2245
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    The infrared multiple-photon decomposition of β-propiolactone was found to give only ethylene and carbon dioxide with the same yield as the products, where the material balance was above 90%. This result suggests that the unimolecular decomposition into ethylene and carbon dioxide is a unique reaction channel of the compound at highly vibrationally excited states. It was shown that the decomposition probability was strongly dependent on the fluence but slightly dependent on the pressure.
  • Kenzo Hiraoka, Hajime Takimoto, Kazuya Morise, Takashi Shoda, Shizuo N ...
    1986 年 59 巻 7 号 p. 2247-2254
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    The ion/molecule reactions in acetone were investigated which were induced by the electron impact. It was found that the protonated acetone reacts with an acetone molecule to produce the protonated diacetone alcohol (4-hydroxy-4-methyl-2-pentanone) and the protonated mesityl oxide (4-methyl-3-penten-2-one) through the aldol condensation reaction. It was also found that the acetone molecule isomerizes from keto to enol form in the interaction with the chloride ion. The thermochemical data for the higher-order clustering reactions of the proton and chloride ion with acetone molecules were obtained.
  • Morio Yashiro, Masanobu Ajioka, Shigenobu Yano, Koshiro Toriumi, Tasuk ...
    1986 年 59 巻 7 号 p. 2255-2261
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    The crystal and molecular structures of (−)546-((R)-alaninato)((6R,8R)-6,8-dimethyl-2,5,9,12-tetraazatridecane)cobalt(III) bromide trihydrate ((−)546-[Co(R-ala)(1,5R,7R,11-Me4-2,3,2-tet)]Br2·3H2O) (1), derived from (−)546-[Co(AMM)(1,5R,7R,11-Me4-2,3,2-tet)]+ on decarboxylation, have been determined from three-dimensional X-ray counter data. In the above, AMM is an α-amino-α-methylmalonate ion. The compound crystallizes in an orthorhombic space group P212121 with a=11.713 (1) Å, b=20.301 (2) Å, c=10.113 (2) Å, and Z=4. The structure was solved by the heavy-atom method followed by full-matrix least-squares and Fourier techniques. A refinement using 2168 reflections with |Fo|>3[σ(Fo)] gave R=0.052. The absolute configuration of the complex cation is Λ in the β2 form. The gauche conformations of two five-membered chelate rings for the tetramine are both δ, and the central six-membered chelate ring adopts a chair conformation with one methyl group axial and the other equatorial. All the secondary nitrogen atoms have S configurations except one of the terminal nitrogen atoms whose absolute configuration is R. The N-methyl group in an “out-of-plane” five-membered chelate ring is equatorial; however, the other in an “in-plane” five-membered chelate ring has an axial disposition. The alaninate ion coordinates to the cobalt via N and O atoms. The absolute configuration around the carbon center of the alanine was found to be R.
  • Yoshinori Uwamino, Akira Tsuge, Toshio Ishizuka, Hideo Yamatera
    1986 年 59 巻 7 号 p. 2263-2267
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    Rare earth (RE) halides (fluorides, chlorides, bromides, and iodides) have been studied by X-ray photoelectron spectroscopy. The binding energies (BE’s) of the RE 3d and 4d peaks for the chlorides, bromides, and iodides are related to the atomic charge calculated on the basis of Pauling’s scale of electronegativity (Pauling charge). Except for Y and Lu, the observed RE 3d and 4d BE’s for the fluorides are lower than those expected. For Y and Lu, the observed RE 3d and 4d BE’s for all halides are related to the Pauling charge. For the fluorides and chlorides, the BE’s of the ligand peak show variations with increasing atomic number of RE’s and a specific “tetrad effect” is observed in plots of BE versus RE atomic number and versus 1/R (where R is the mean distance from the ligand atom to the neighboring RE atom), except for the BE’s of the F 1s peaks from the light RE fluorides. For the iodides and bromides, no or little characteristic variations are seen in the BE’s of I and Br.
  • Isao Sanemasa, Yuko Nishimoto, Akira Tanaka, Toshio Deguchi
    1986 年 59 巻 7 号 p. 2269-2272
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    Iodine molecules, which are volatile, are expelled from an aqueous medium into the gaseous phase by introducing an inert gas at a constant flow rate into the aqueous phase, and the amount of the released iodine is measured as a function of aeration time. In the presence of a nonvolatile solute which associates with molecular iodine, the releasing rate of the volatile solute is reduced with increasing degree of the association between both the solutes in the aqueous medium. The method was applied to the case of association of iodine with α-, β-, or γ-cyclodextrin; the formation constants of the three 1:1 complexes are (1.5±0.1)×104, (1.5±0.2)×102, and 24±3 dm3 mol−1, respectively, at 25.0 °C and low ionic strengths. The complexation of iodine with iodide or bromide ion was also studied; the I3 and I2Br formation constants are (6.5±0.1)×102 and 16±1 dm3 mol−1, respectively, at 25.0 °C and I=0.1(NaClO4).
  • Yuzo Tamari, Kimio Nishimura, Haruo Tsuji, Yuzuru Kusaka
    1986 年 59 巻 7 号 p. 2273-2278
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    Vertical concentration distributions of arsenite and arsenate in a reservoir (depth, ≈31 m) and its bottom sediment (core depth, ≈18 cm) have been investigated. The concentrations of arsenite and arsenate in the water were determined by a spectrophotometric method, and those in the sediment were also determined by the same method after the following leaching-treatments of the sediment. The leaching of arsenic from the sediment was carried out by using three solutions; (1) 0.1 M hydrochloric acid (acid-soluble fraction), (2) 1 M sodium hydroxide solution (alkali-soluble fraction), and (3) hydrofluoric and perchloric acid mixture (silicate fraction). It was found that arsenic was rich in the surface layer of the sediment, and most of it existed as arsenite fixed with iron hydroxide. Based on the analytical and leaching results of arsenic, iron, manganese, zinc, copper, and others in the reservoir and in its sediment respectively, the sedimentation process of arsenic from the reservoir and its dissolution process from the sediment have been discussed.
  • Isao Hasegawa, Kazuyuki Kuroda, Chuzo Kato
    1986 年 59 巻 7 号 p. 2279-2283
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    The effect of the addition of tetramethylammonium, (2-hydroxyethyl)trimethylammonium and benzyltrimethylammonium ions on the distribution of the silicate anions arising from the hydrolysis of tetraethoxysilane was studied by using the trimethylsilylation method. The selective formation of the octameric silicate anion with a double four-membered cage was confirmed in these solutions. It was found that tetraalkylammonium ions with three methyl groups, whether or not the other group was a methyl group, contributed to the formation of a double four-membered cage octamer.
  • Yoshichika Tajiri, Hisanobu Wakita
    1986 年 59 巻 7 号 p. 2285-2291
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    The coordination structure of copper(II) ions in aqueous and methanolic solutions was investigated by means of EXAFS spectroscopy. The hexaaquacopper(II) complex in the aqueous Cu(ClO4)2 solution had an elongated octahedral structure, with four equatorial distances of 2.00 Å and two axial distances of 2.28 Å. Scarcely no axial interaction has been seen in the radial-distribution curve after the Fourier transform of the EXAFS spectrum, for the real and imaginary parts of the Fourier transformed function for the axial interactions are diminished by the interference of those for the equatorial interactions. Two distances for the equatorial interactions of the mixed-ligand chlorocopper(II) complexes in the methanolic CuCl2 solution were clearly resolvable in the radial-distribution curve; they were 2.00 Å and 2.22 Å for the Cu–O and Cu–Cl interactions respectively.
  • Kousaburo Ohashi, Hidetoshi Shoji, Katsumi Yamamoto
    1986 年 59 巻 7 号 p. 2293-2297
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    The kinetics and mechanism of the extraction of nickel(II) with 3-mercapto-1,5-diphenylformazan (dithizone, Hdz) into chloroform in the presence of 1,10-phenanthroline (phen) or pyridine (py) were studied in the presence of 0.1 mol dm−3 or 0.2 mol dm−3 NaNO3 at 25 °C. For the nickel(II)–dithizone–1,10-phenanthroline system, the rate-determining steps were the competitive reactions of nickel(II) with dithizonate and with 1,10-phenanthroline in an aqueous phase. The second-order rate constants for the formation of [Ni(dz)]+ and of [Ni(phen)]2+ were determined to be (6.0±0.4)×103 mol−1 dm3 s−1 and (3.4±0.2)×103 mol−1 dm3 s−1 respectively. It was suggested that [Ni(phen)]2+ is more reactive toward dithizonate than toward 1,10-phenanthroline in an aqueous phase. The formation of [Ni(phen)2]2+ retards the extraction of nickel(II) with dithizone. For the nickel(II)–dithizone–pyridine system, the rate-determining step is probably the reaction of [Ni(py)]2+ with dithizonate in an aqueous phase. The second-order rate constant for this reaction was determined to be (1.7±0.3)×105 mol−1 dm3s−1.
  • Masahiro Taniguchi, Mamoru Shimoi, Akira Ouchi
    1986 年 59 巻 7 号 p. 2299-2302
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    The crystal and molecular structure of the title complex was determined by a single-crystal X-ray diffraction technique. The crystal is triclinic with a space group P\bar1, a=11.323(4), b=18.383(10), c=9.284(5) Å, α=104.62(4), β=114.26(3), γ=77.71(4)°, Z=4; the final R value obtained was 0.034. All cadmium atoms are lined approximately along the [111] axis and each pair of metal atoms are bridged by two thiocyanate ions (SCN), one of which is S-coordinated and the other is N-coordinated to the same side metal atom. Also bonded with two nitrogen atoms of 4-methylpyridine (pic) ligands, the metal atom is 4N2S-hexa-coordinated and is in an octahedral geometry. The cadmium atoms, where the ligated respective pairs of N(SCN), N(pic), and S(SCN) atoms are all in a trans configuration, and the metal atoms where the ligated respective pairs of N(pic) and S(SCN) are in cis, while the pair of the N(SCN) in trans configuration, appear alternatively in the polymer chain.
  • Hiroshi Fukutomi, Hideki Ohno, Hiroshi Tomiyasu
    1986 年 59 巻 7 号 p. 2303-2308
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    The kinetics of ligand-exchange reactions between tetrakis(acetylacetonato)uranium(IV) [U(acac)4] (acac=acetylacetonate) and free acetylacetone Hacac in various organic solvents, CDCl3, C6D6, and CD3CN has been studied by 1H NMR. The rate laws were found to change remarkably with these solvents used. The observed first-order rate constant kobsd in CDCl3 depended linearly on the concentration of free Hacac in the enol form as kobsd=ks[Hacac]enol, while the plots of kobsd vs. [Hacac]enol in C6D6 deviated from straight lines in higher concentrations of Hacacenol. The exchange rate was much slower in CD3CN than in CDCl3 and C6D6, and kobsd increased only slightly with [Hacac]enol. Addition of dimethyl sulfoxide (DMSO) in C6D6 yielded the retardation of exchange rate giving a rate law kobsd−1=p+q[DMSO], where p and q are constants. From the results obtained in these solvents, a mechanism passing through nine-coordinate intermediates was proposed.
  • Yoshinori Ihara, Akiko Wada, Yutaka Fukuda, Kozo Sone
    1986 年 59 巻 7 号 p. 2309-2315
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    Nickel(II) complexes of 1,2-butanediamine(1,2-bn) and 3,3-dimethyl-1,2-butanediamine(dmbn), were prepared, and their thermal behavior was investigated in solid phase. The original complexes were all violet, octahedral diaquabis(diamine) complexes([Ni(H2O)2(1,2-bn/dmbn)2]X2; X=Cl, Br, NO3, or ClO4). The 1,2-bn complexes with Cl or Br and the dmbn complex with NO3 showed a two-step thermochromism, violet→yellow→violet blue, upon heating. These steps correspond to structural changes to a square planar anhydride, and then to an octahedral dianiono complex. The complexes of both ligands with ClO4 underwent only thermal deaquation, changing into orange square planar anhydride. Other salts, the 1,2-bn complex with NO3 and the dmbn complexes with Cl or Br, were converted into octahedral dianiono complexes by thermal deaquation-anation which occurs in one step. The differences among the thermal reactivities of the complexes with different diamines can be understood on the basis of steric hindrance caused by the substituent groups on the diamine.
  • Yoshihiro Ohba, Shinji Kubo, Masaaki Nakai, Atsunori Nagai, Masayo Yos ...
    1986 年 59 巻 7 号 p. 2317-2320
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    Thermolysis of several p-substituted aryl azides (p-R-C6H4N3; R=COCH3, CO2CH3, COPh) in methanol gave 5-substituted 2-methoxy-3H-azepines in moderate yields. Thermolysis of m-substituted aryl azides (m-R-C6H4N3; R=COCH3, CO2CH3, COPh, NO2) gave 4-substituted 2-methoxy-3H-azepines and 6-substituted 2-methoxy-3H-azepines in good yields. In contrast, thermolysis of p-azidoacetophenone in piperidine gave 5-acetyl-2-piperidino-3H-azepine and an unusual product, 6-acetyl-2-piperidino-3H-azepine, and p-aminoacetophenone.
  • Yoichi Taguchi, Yasuo Suhara
    1986 年 59 巻 7 号 p. 2321-2324
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    The reaction of 2,2-dimethylthiirane (4) with diethyl malonate (5) in the presence of sodium ethoxide gave 3-ethoxycarbonyl-5,5-dimethyl-dihydro-2(3H)-thiophenone (6) and a polymer. The yield of 6 could be increased to 65%. The reaction of thiirane, 2-methylthiirane, 2-butylthiirane, 2-hexylthiirane, 1,2-epithiocyclohexane, and 2-phenylthiirane with 5 also gave corresponding dihydro-2(3H)-thiophenone derivatives. Although the reaction of an alkyl-substituted thiirane with 5 selectively gave a product formed by an attack of a carbanion at the less-hindered carbon of the thiirane ring, the major product of the reaction of 2-phenylthiirane with 5 was an isomer formed by an attack at the more hindered carbon of the thiirane ring. The reaction of 4 with ethyl acetoacetate gave 3-acetyl-5,5-dimethyl-dihydro-2(3H)-thiophenone selectively. A product 6 was also obtained by a reaction of 4 with 5 by using sodium hydride instead of sodium ethoxide.
  • Yoko Kuwae, Mikiharu Kamachi, Koichiro Hayashi, Heinz G. Viehe
    1986 年 59 巻 7 号 p. 2325-2330
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    The halogen-abstraction reactions of carbon radicals were investigated as a model of the chain-transfer reaction in the radical polymerization of vinyl compounds. The kinetics of the halogen-abstraction reaction of carbon radicals ((CH3)2\dotCX, X=OC6H5, OCOCH3, SC6H5, C6H5, and CN) from tetrahalomethanes(CBr4, CBrCl3, CCl4) were studied in toluene at 80 °C by the ESR method using 2-(t-butyl)thioacrylonitrile as a spin-trapping reagent. The reactivity of these radicals for each halomethane decreased in the order X: OC6H5>OCOCH3>SC6H5>C6H5>CN The reactivity of tetrahalomethanes for each radical decreased in the order CBr4>CBrCl3>CCl4. Results are explained by taking into account the electron-transfer process from carbon radicals to tetrahalomethanes. Absolute rate constants of the halogen abstraction of (CH3)2\dotCCN and (CH3)2\dotCC6H5 from CBr4 and CBrCl3, and of their additions to 2-(t-butylthio)acrylonitrile were estimated by the spin-trapping method, and they were compared with available data for similar reactions.
  • Tadashi Shiraiwa, Hideya Miyazaki, Yoshihiro Sakamoto, Hidemoto Kuroka ...
    1986 年 59 巻 7 号 p. 2331-2334
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    Racemic structures of the butylammonium salt, pentylammonium salt, benzylammonium salt, dicyclohexylammonium salt(DL-DCH salt), and 4-methylpiperidinium salt(DL-4-MP salt) of N-formyl-DL-phenylalanine were studied to explore the possibility of optical resolution by preferential crystallization. Free energies of formation of racemate (ΔGF) of the DL-salts and data at eutectic points in binary phase diagrams of melting points indicate that the DL-salts form racemic compounds in the vicinity of the melting points. However, according to ΔGF of DL-DCH and 4-MP salts and infrared spectra and solubilities of the DL- and L-salts, these DL-salts transform into conglomerates around room temperature. It is possible to resolve DL-DCH and 4-MP salts by preferential crystallization at 10 °C. Successive preferential crystallization of DL-4-MP salt at 10 °C in 1-butanol gives the D- and L-salts with optical purities of 95–100%.
  • Shigeru Futamura, Yoshio Kamiya
    1986 年 59 巻 7 号 p. 2335-2340
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    Triggering materials responsible for coloring of coal liquids have been searched by comparing the structures of the colored materials derived from the neutrals, acids, and bases of the coal liquid and the nitrogenous model compounds. Basic constituents of the coal liquid are most prone to photooxidation and afford colored materials of higher molecular weight and stronger absorption in the visible region. Model compound studies suggest that they are predominantly formed in the photoinduced oxidative coupling of aromatic amines.
  • M. V. Ramanamurti, P. V. S. S. Prabhu, S. L. Bahadur
    1986 年 59 巻 7 号 p. 2341-2345
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    Precise viscosity data for aqueous binary mixtures of ethylene glycol (EG), 2-methoxyethanol (ME), and 1,2-dimethoxyethane (DME) at different mole fractions and at various temperatures are presented. EG behaves as a structure breaker showing negative deviation in viscosity–composition curve. Hydrophobic solutes ME and DME showed typical maximum in viscosity–composition curve in water rich region; attributed to the existence of “microheterogeniety” in these mixtures.
  • Harumichi Kobashi, Tomoyuki Kondo, Masa-aki Funabashi
    1986 年 59 巻 7 号 p. 2347-2348
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    The triplet exciplex between chloranil (CA) and durene (DH) shows a decay which is associated with solvent viscosity rather than polarity, in spite of having a full charge-transfer (CT) character.
  • Takashi Masuda, Kazuhisa Murata, Toshiaki Kobayashi, Akio Matsuda
    1986 年 59 巻 7 号 p. 2349-2350
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    The Rh4(CO)12/N-methyl-2-pyrrolidone system is featured in that the rate of ethylene glycol (EG) formation is significantly accelerated with increasing reaction temperature. The turnover frequency of EG at 300 °C and 2000 kg/cm2 (H2/CO=1) is about 2000 h−1. The Rh4(CO)12/tributylamine system also has a high catalytic activity at a high temperature.
  • Yukio Hoshino, Toshinori Oohinata, Noboru Takeno
    1986 年 59 巻 7 号 p. 2351-2352
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    Flavone was obtained by a reaction of 2′-hydroxychalcone with disulfides in good yield. Among several disulfides, diphenyl disulfide gave the best result. Under the same conditions, some flavones were obtained from the corresponding 2′-hydroxychalcones in satisfactory yields.
  • Pierre Duhamel, Mitsuharu Kotera, Thierry Monteil
    1986 年 59 巻 7 号 p. 2353-2355
    発行日: 1986年
    公開日: 2006/06/27
    ジャーナル フリー
    The 2,2-bifunctionalized piperidines 6 and 10 were obtained via ring contraction of the seven-membered heterocyclic enamino aldehyde 5 in nearly quantitative yield. The synthesis of 1-benzyl-1-azaspiro[5.5]undec-7-en-9-one 9 (a formal precursor of perhydrohistrionicotoxin 1b) in 3 steps from the piperidinedialdehyde monoacetal 6, is reported.
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