Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 79 , Issue 10
Showing 1-19 articles out of 19 articles from the selected issue
Award Accounts
The Chemical Society of Japan Award for Creative Work for 2004
  • Mahendra P. Kapoor, Shinji Inagaki
    2006 Volume 79 Issue 10 Pages 1463-1475
    Published: 2006
    Released: October 10, 2006
    JOURNALS FREE ACCESS
    The latest developments in periodic mesoporous organosilicas (PMO) have been compiled. The discovery of mesoporous hybrid organosilicas with molecular scale periodicity resulting from alternating hydrophilic and hydrophobic layers, and a cost effective solution showing the use of allyl derivatives of the bis-silyl precursors are discussed. Relevant uses of the periodic mesoporous materials in diverse applications are summarized. For example, the metal-incorporated periodic mesoporous organic frameworks are likely to offer an advantage in catalytic transformations, while the functionalized PMOs show promise in fascinating catalytic applications via enhancing the physical properties of guest molecules and clusters. In general, the advancement in PMOs have showed great promise and are expected to deliver exciting achievable future findings.
  • Ilhyong Ryu, Yoshitaka Uenoyama, Hiroshi Matsubara
    2006 Volume 79 Issue 10 Pages 1476-1488
    Published: 2006
    Released: October 10, 2006
    JOURNALS FREE ACCESS
    The carbonylation of vinyl radicals gives α,β-unsaturated acyl radicals. This transformation was successfully applied to tandem radical reactions, resulting in assembling three and four components. In these reactions, both halogen abstraction from vinyl halides and hetero atom radical additions to alkynes are used to generate the parent vinyl radicals. Ab initio calculations and density functional methods predict that α,β-unsaturated acyl radicals and the isomeric α-ketenyl radicals are not canonical forms, but are isomeric species that undergo interconversion. Calculations also indicate that α,β-unsaturated acyl radicals are more stable than α-ketenyl radicals, whereas α-ketenyl radicals containing a heteroatom, such as Si, Ge, and Sn, at α-position are more stable than the corresponding α,β-unsaturated acyl radicals. This represents a promising resource for developing new synthetic applications that involve the use of the α-ketenyl radicals. Indeed, following the prediction by calculation, we succeeded in trapping of a tin-attached α-ketenyl radical by imines and amines in an intramolecular fashion. We were also able to achieve the intermolecular trapping of α-ketenyl radicals, providing a new method for alkyne carbonylation by hybrid radical/ionic reactions.
BCSJ Award Article
  • Kei Ohkubo, Takashi Nanjo, Shunichi Fukuzumi
    2006 Volume 79 Issue 10 Pages 1489-1500
    Published: 2006
    Released: October 10, 2006
    JOURNALS FREE ACCESS
    Photooxygenation of triphenylphosphine (Ph3P) to triphenylphosphine oxide (Ph3P=O) with molecular oxygen (O2) occurs under photoirradiation of 9-mesityl-10-methylacridinium perchlorate ([Acr+–Mes]ClO4) which acts as an efficient electron-transfer photocatalyst. Photooxidation of benzylamine (PhCH2NH2) with O2 also occurs efficiently under photoirradiation of Acr+–Mes to yield PhCH2N=CHPh and hydrogen peroxide (H2O2). Each photocatalytic reaction is initiated by intramolecular photoinduced electron transfer from the Mes moiety to the singlet excited state of the Acr+ moiety to produce the electron-transfer state (Acr–Mes•+). The Mes•+ moiety oxidizes Ph3P and PhCH2NH2 to produce the radical cations (Ph3P•+ and PhCH2NH2•+, respectively), whereas the Acr moiety reduces O2 to O2•−. The produced Ph3P•+ binds with O2•− as well as O2, leading to the oxygenated product (Ph3P=O). On the other hand, proton transfer from PhCH2NH2•+ to O2•− occurs, followed by hydrogen transfer, leading to the dehydrogenated dimer product, PhCH2N=CHPh. In each case, the radical intermediates were detected by laser flash photolysis and ESR measurements to clarify the photocatalytic mechanism.
Articles
  • Keishi Ohara, Yoko Ichimura, Kumi Tsukamoto, Mayumi Ogata, Shin-ichi N ...
    2006 Volume 79 Issue 10 Pages 1501-1508
    Published: 2006
    Released: October 10, 2006
    JOURNALS RESTRICTED ACCESS
    A kinetic study involving 4-hydroxycinnamic acid derivatives (HCAs) was performed in order to clarify the mechanism for free radical-scavenging and vitamin E-regenerating. The second-order rate constants of the radical-scavenging reaction (ks) observed for caffeic acid derivatives are larger than those for ferulic acid derivatives. The result may be explained by i) the lower oxidation potential coming from the existence of the more electron-donating hydroxy group comparing with methoxy group, and ii) the stabilization effect of the corresponding radicals produced in the radical-scavenging reaction through intramolecular hydrogen bonding. The radical-scavenging activity of HCAs in ethanol mainly occurs via the hydrogen atom transfer from the phenolic OH-protons. The pH dependence of ks for ferulic acid in the aqueous Triton X-100 micelle solutions suggests the importance of the phenolic OH proton on the radical-scavenging reaction. On the other hand, the pH dependence of ks for caffeic acid and chlorogenic acid suggests the occurence of intramolecular hydrogen bonding and an electron-transfer process in the radical-scavenging reaction.
  • Kazuyasu Ibuki, Masakatsu Ueno
    2006 Volume 79 Issue 10 Pages 1509-1518
    Published: 2006
    Released: October 10, 2006
    JOURNALS RESTRICTED ACCESS
    Molecular dynamics (MD) simulations are performed for a simple diffusion-controlled reaction in a hard-sphere fluid. The short-time transient rate constants are compared with the Markovian Langevin dynamics (LD), two theories based on the Fokker–Planck–Kramers equation (FPKE), and the Smoluchowski–Collins–Kimball (SCK) theory based on the diffusion equation. At n* = 0.7856, where n* is the total number density reduced by the diameter of the molecules, molecular motions are diffusive and Markovian, and the MD results agree well with the LD results. At n* = 0.9428, the MD results are much larger than the LD ones at short times, and the discrepancy can be explained by non-Markovian effects. Also at n* = 0.2000, where inertia effects are important, the time profile of the MD rate constant is satisfactorily explained by LD, while the MD rate constant shows a smaller decay than at higher densities. FPKE theory with a continuous velocity distribution reproduces the LD results under all conditions indicating that the theory is valid over a wide density range. FPKE theory with a discontinuous velocity distribution cannot explain the simulation results at the lowest density despite taking into account inertia effects. Although SCK theory is expected to be valid only at high densities, the predicted rate constant is close to that from the simulation even at the lowest density, if the intrinsic rate constant is chosen to reproduce the exact value of the initial rate constant.
  • Ling Jiang, Qiang Xu
    2006 Volume 79 Issue 10 Pages 1519-1524
    Published: 2006
    Released: October 10, 2006
    JOURNALS RESTRICTED ACCESS
    Reactions of zinc and cadmium atoms with ammonia molecules in a solid argon matrix have been studied by infrared spectroscopy. MNH3 (M = Zn and Cd) was found from the reaction of ammonia with excited metal atoms, similar to the reaction of ammonia with Hg atom, but quite different from those with other metal atoms (Sc, Ti, V, etc.). The absorptions peaks of HZnNH2 sharply increased upon broad-band irradiation, whereas there was no detectable HCdNH2 produced under the same experimental conditions. Density functional theory calculations were performed on these molecules and the transition states. The agreement between experimental and calculated vibrational frequencies, relative absorption intensities, and isotopic shifts provides strong support for the identification of the products. Furthermore, energetic analysis for possible reaction paths of these reactions is also given.
  • Mari Toyama, Ken-ichi Inoue, Shinobu Iwamatsu, Noriharu Nagao
    2006 Volume 79 Issue 10 Pages 1525-1534
    Published: 2006
    Released: October 10, 2006
    JOURNALS RESTRICTED ACCESS
    The reaction between trans-[RuCl2(dmso-S)4] (dmso = dimethyl sulfoxide) and 2,2′-bipyridine (bpy) in EtOH–H2O afforded trans(Cl),cis(S)-[RuCl2(bpy)(dmso-S)2] (1) in good yield. When dissolved in DMSO, 1 rearranged to the thermodynamically more stable cis(Cl),cis(S)-[RuCl2(bpy)(dmso-S)2] (2) along with a small amount of cis(Cl),trans(S)-[RuCl2(bpy)(dmso-S)2] (3). Isomer 2 was selectively synthesized by heating 1 in EtOH–DMSO (9:1) and, more conveniently, by the reaction of cis(Cl),fac(S)-[RuCl2(dmso-S)3(dmso-O)] with bpy in EtOH–DMSO (9:1). The structures of 1, 2, and 3 were determined using single-crystal X-ray crystallography. The crystal structure of 1 revealed that the 6- and 6′-protons of the bpy ligand repulsed the two dmso ligands within the equatorial plane, resulting in the lower thermodynamic stability of 1. In contrast, the crystal structure of 2 showed that its bpy ligand is involved in hydrogen bonding with the monodentate dmso and Cl ligands within the equatorial plane. Our studies show that hydrogen bonds within the equatorial plane of 2 restrict the conformation of the dmso ligands in the crystal and in DMSO.
  • Rei Okamura, Tohru Wada, Koji Tanaka
    2006 Volume 79 Issue 10 Pages 1535-1540
    Published: 2006
    Released: October 10, 2006
    JOURNALS RESTRICTED ACCESS
    A platinum–ruthenium dinuclear complex, [(PtCl){RuCl(tBu2sq)}(btpyxa)]2+ ([2]2+) (btpyxa = 2,7-di-tert-butyl-9,9-dimethyl-4,5-bis(2,2′:6′,2″-terpyrid-4′-yl)xanthene, tBu2sq = 3,5-di-tert-butyl-1,2-benzosemiquinonate ion), in which btpyxa acts as a bridging ligand, was prepared, and its physical properties were compared to those of an analogous dmso complex, [(PtCl){Ru(tBu2sq)(dmso)}(btpyxa)]2+ ([1]2+) (dmso = dimethyl sulfoxide). Treatment of complex [1]2+ with an aqueous NaOH solution followed by 2-aminoethanethiol afforded [{Pt(SCH2CH2NH2)}{Ru(tBu2sq)(dmso)}(btpyxa)]2+ ([3]2+). On the other hand, the reaction of complex [2]2+ with 2-aminoethanethiol produced [{Pt(SCH2CH2NH2)Ru(tBu2sq)}(btpyxa)]2+ ([4]2+), in which Pt and Ru atoms are bridged by the 2-aminoethanethiolato ligand. Complex [4]2+ was also obtained by heating complex [3]2+ in 2-methoxyethanol.
  • Shah Raj Ali, Kamaluddin
    2006 Volume 79 Issue 10 Pages 1541-1546
    Published: 2006
    Released: October 10, 2006
    JOURNALS RESTRICTED ACCESS
    Metal cyanogen complexes have been proposed to be efficient prebiotic catalysts. Insoluble metal cyanogen complexes are thought to have concentrated biomonomers from dilute prebiotic soup which facilitated a class of prebiotic reactions. Thus, large biopolymers were able to form during the course of chemical evolution and the origin of life. Based on this hypothesis, the interaction of two naturally occurring α-aromatic amino acids, tryptophan and phenylalanine, with cobalt(II), copper(II), and cadmium(II) hexacyanochromate(III) has been studied, and the interaction was found to be strongest at neutral pH (≈7.0). Cobalt(II) hexacyanochromate(III) adsorbed the largest amount of both amino acids while tryptophan had a stronger affinity than phenylalanine. Infrared spectral studies of the metal hexacyanochromate(III) complexes, amino acids and metal hexacyanochromate(III)–amino acid adducts indicated the involvement of NH2 as well as COO groups of amino acids and surface metal ions present in the lattice of the metal hexacyanochromate(III) complexes.
  • Shin-Pin Chen, Chih-Hua Chao, Ho-Cheng Huang, Yang-Chang Wu, Chung-Kua ...
    2006 Volume 79 Issue 10 Pages 1547-1551
    Published: 2006
    Released: October 10, 2006
    JOURNALS RESTRICTED ACCESS
    Seven new β-caryophyllene-derived terpenoids (17) were isolated from EtOAc extracts of the Formosan soft coral Sinularia gibberosa. The structures of compounds 17 were elucidated on the basis of extensive spectroscopic analyses and by comparison with the spectral data of related metabolites. Cytotoxicity evaluation of the above metabolites towards a limited panel of cancer cell lines also will be described.
  • Mitsuru Kitamura, Yuichiro Ihara, Kazuyoshi Uera, Koichi Narasaka
    2006 Volume 79 Issue 10 Pages 1552-1560
    Published: 2006
    Released: October 10, 2006
    JOURNALS RESTRICTED ACCESS
    Peduncularine, the principal alkaloid of the Tasmanian shrub Aristotelia peduncularis, was synthesized via the radical cyclization of 7-oxabicyclo[2.2.1]hept-2-en-5-yl ketone oxime 9 forming the 6-azabicyclo[3.2.1]octane skeleton.
  • Mostafa A. S. Hammam, Hiroshi Nakamura, Yukari Hirata, Htoi Khawn, Yas ...
    2006 Volume 79 Issue 10 Pages 1561-1572
    Published: 2006
    Released: October 10, 2006
    JOURNALS RESTRICTED ACCESS
    Total syntheses of biliverdin derivatives with a Z-syn, Z-anti, or E-syn CD-ring components were accomplished via new and efficient methods for the construction of sterically locked CD-ring components towards the elucidation of the stereochemistry of the chromophore in phytochromes.
  • Nobuhiro Takeda, Taro Tanabe, Norihiro Tokitoh
    2006 Volume 79 Issue 10 Pages 1573-1579
    Published: 2006
    Released: October 10, 2006
    JOURNALS RESTRICTED ACCESS
    Novel silacyclic compounds containing a titanium and some chalcogen atoms, [Tbt(Mes)Si(μ-Ch)2TiCp2] and [Tbt(Mes)Si(μ-Ch)(μ-Ch2)TiCp2] (Ch = S and Se; Tbt = 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl; Mes = mesityl; Cp = cyclopentadienyl), were synthesized by the reactions of the disilene Tbt(Mes)Si=Si(Mes)Tbt with the corresponding [Cp2TiCh5] (Ch = S and Se). The spectroscopic properties of these compounds are presented together with the results of theoretical calculations.
  • Kazuhiro Kobayashi, Kazuna Miyamoto, Tohru Yamase, Daizo Nakamura, Osa ...
    2006 Volume 79 Issue 10 Pages 1580-1584
    Published: 2006
    Released: October 10, 2006
    JOURNALS RESTRICTED ACCESS
    A convenient synthetic method for 1-aryl-1H-indole derivatives has been developed. 2-(Arylamino)-α-methylstyrene derivatives were treated with iodine in the presence of sodium hydrogencarbonate to give 1-aryl-3-methyl-1H-indole derivatives in fair to good yields. 3-Ethyl-2-methyl-1-phenyl-1H-indole and 3,3′-dimethyl-1,1′-(p-phenylene)diindole were also prepared from the respective 2-(phenylamino)styrene derivatives under the same conditions in reasonable yields.
  • Gaku Yamamoto, Ai Koseki, Jun Sugita, Hisashi Mochida, Mao Minoura
    2006 Volume 79 Issue 10 Pages 1585-1600
    Published: 2006
    Released: October 10, 2006
    JOURNALS RESTRICTED ACCESS
    Deamination reactions of 1-alkyl-9-aminomethyltriptycenes (alkyl = Me, Et, i-Pr, and t-Bu) and 9-(1-aminoethyl)-1-methyltriptycene were performed in CHCl3 and in AcOH, and product distributions were studied. The results suggest that the loss of N2 from a primary alkanediazonium ion predominantly takes place concomitantly with participation of a C–H bond of the neighboring 1-alkyl group to form a nonclassical cationic species with a three-center two-electron bonding, while the loss of N2 from a secondary alkanediazonium ion occurs spontaneously to form a secondary carbocation. Solvent effects (CHCl3 vs AcOH) are explained in terms of lower nucleophilicity/basicity of the AcO in AcOH than in CHCl3 due to solvation.
  • Suman L. Jain, Vishal B. Sharma, Bir Sain
    2006 Volume 79 Issue 10 Pages 1601-1603
    Published: 2006
    Released: October 10, 2006
    JOURNALS RESTRICTED ACCESS
    A variety of primary and secondary alcohols have been oxidized to the corresponding aldehydes and ketones in excellent yields with aqueous 30% hydrogen peroxide by using methyltrioxorhenium and sodium bromide as a catalyst system and the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim]BF4) as a recyclable green solvent.
  • Khodayar Gholivand, Zahra Shariatinia, Fariba Yaghmaian, Halin Faramar ...
    2006 Volume 79 Issue 10 Pages 1604-1606
    Published: 2006
    Released: October 10, 2006
    JOURNALS RESTRICTED ACCESS
    New 1,3,2-diazaphosphorinanes with the formula (X = F (1), Cl (2), Br (3), and I (4)) were synthesized and characterized by 1H, 13C, and 31P NMR and IR spectroscopy, and elemental analysis. The structures have been determined for compounds 3 and 4 by X-ray crystallography.
  • Yuko Takeoka, Keisuke Asai, Masahiro Rikukawa, Kohei Sanui
    2006 Volume 79 Issue 10 Pages 1607-1613
    Published: 2006
    Released: October 10, 2006
    JOURNALS RESTRICTED ACCESS
    Two-dimensional layered perovskite compounds, (CnH2n+1NH3)2(CH3NH3)m−1PbmX3m+1 (n = 2, 3, 4, 6, and 10; X = Cl, Br, and I; m = 1, 2, and 3) were systematically prepared. The influences of the barrier-size, halide species, and well thickness of the perovskite thin films on the quantum confinement structures were investigated. The layered perovskite films showed a strong and clear absorption peak due to excitons confined in inorganic quantum-wells. The exciton peak shifted to lower energy as the halide species was changed from Cl to Br and I. Furthermore, fine multilayer perovskite compound films were prepared by varying the spin-coating conditions.
  • Yun-Xing Yan, Hai-Hua Fan, Chi-Keung Lam, Hong Huang, Jing Wang, Sheng ...
    2006 Volume 79 Issue 10 Pages 1614-1619
    Published: 2006
    Released: October 10, 2006
    JOURNALS RESTRICTED ACCESS
    Two new heterocycle-based two-photon absorption chromophores, 4-[4-(4,5-diphenyl-1H-imidazol-2-yl)styryl]pyridine (2) and (E)-4-{[2-(1H-benzimidazol-2-yl)vinyl]styryl}-N-methylpyridinium iodide (4), have been synthesized and characterized. The two molecules possess A–π–A′ structures. A π-deficient heteroaromatic ring (benzimidazole, 4,5-diphenyl-1H-imidazole) is used as an acceptor (A), and a pyridine ring is used as another acceptor (A′). One-photon-excited fluorescence, one-photon-fluorescence quantum yields, two-photon-excited fluorescence, and two-photon absorption cross-sections were investigated. Pumped with 740 and 800 nm laser excitation, compounds 2 and 4 had two-photon absorption cross-sections (41 and 38 GM) and two-photon-excited fluorescence (511 and 601 nm) in DMF, respectively. The crystal structure of compound 4 was determined by using X-ray single-crystal diffraction analysis.
feedback
Top