Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
91 巻 , 4 号
選択された号の論文の22件中1~22を表示しています
 
  • Tokihiro Tanaka, Hiroki Asakura, Rie Fujiwara, Kentaro Kumamoto, Hiroa ...
    2018 年 91 巻 4 号 p. 507-514
    発行日: 2018/04/15
    公開日: 2018/04/15
    ジャーナル 認証あり

    An improved synthesis of the A–E ring segment of ciguatoxin CTX3C is described. The E ring segment was synthesized by the intramolecular reaction of allylic stannane and aldehyde with high stereoselectivity. Construction of the A–E ring framework was performed by using the intramolecular allylation of α-acetoxy ether followed by ring-closing metathesis.

  • Xiaoyue Ma, Yongbing Lou, Jinxi Chen
    2018 年 91 巻 4 号 p. 515-522
    発行日: 2018/04/15
    公開日: 2018/04/15
    ジャーナル 認証あり

    Metal-organic frameworks (MOFs) and their heterostructures have been considered as suitable materials for photodegradation of organic pollutants in water treatment. In this work, a series of UiO-66/CuxS composites with different CuxS contents were prepared by using 3-mercaptopropionic acid as a surface-functionalizing agent to anchor CuxS nanoparticles onto UiO-66 surface. The as-synthesized UiO-66/CuxS composites were characterized by using XRD, SEM, TEM, XPS, UV-Vis, PL and the possible growth mechanism of the heterostructure composites was proposed. The UiO-66/CuxS composites were successfully used as photocatalysts for the degradation of Rhodamine B (RhB) under visible-light irradiation. Noticeably, the photocatalytic efficiency of UiO-66/CuxS composites could be tuned by changing Cu/Zr molar ratios. The enhanced photocatalytic activity could be attributed to the synergistic effect between CuxS nanoparticles and UiO-66 frameworks materials. This study provided useful information for the preparation of MOF/semiconductor heterostructure photocatalysts via the surface functionalization method.

  • Manikyanahally N. Kumara, Tesshu Nakahara, Shinjiro Kobayashi, Mizue F ...
    2018 年 91 巻 4 号 p. 523-530
    発行日: 2018/04/15
    公開日: 2018/04/15
    ジャーナル 認証あり

    The decay rate constants of benzhydrylium ions generated by laser irradiation in acetonitrile have been determined photometrically. The decay of the stable carbocation with an electron-releasing substituent was decelerated with addition of LiClO4, being attributed to the decrease of the recombination of the cations with the counter anions. On the contrary, the decay of the highly reactive carbocation was accelerated, indicating the occurrence of the reaction with perchlorate anion. The second-order rate constants (k2) for the reactions of benzhydrylium ions with methanol, ethanol, i-propanol, t-butanol, and water were determined in acetonitrile in the presence of 3 mM LiClO4 for benzhydrylium ions less electrophilic than 3,5-dimethyl-4′-chlorobenzhydrylium ion and in the absence of LiClO4 for the remaining reactive benzhydrylium ions. Their logarithms were linearly correlated with the electrophilicity parameters (E) in Mayr’s equation, log k2 = sN(E + N). Based on the correlations the nucleophilicity parameters (N) were evaluated for these nucleophiles in acetonitrile, MeOH, 6.86; EtOH, 7.13; i-PrOH, 6.82; t-BuOH, 5.35; H2O, 5.79. The low nucleophilicity of t-butanol regardless of its high gas-phase basicity representing the inherent nature in molecular structure suggests the importance of steric environment at the transition state of the combination of benzhydrylium ions with nucleophiles.

BCSJ Award Article
  • Qitao Tan, Patcharin Kaewmati, Shuhei Higashibayashi, Masaki Kawano, Y ...
    2018 年 91 巻 4 号 p. 531-537
    発行日: 2018/04/15
    公開日: 2018/04/15
    ジャーナル 認証あり

    Buckybowls, which are represented by sumanene and corannulene, have attracted considerable attention for their unique bowl structures and interesting physicochemical properties. However, still few heteroatom-doped buckybowls have been reported to date. Here we show the successful synthesis of triazasumanene, an isoelectronic heteroanalogue of sumanene, which possesses a deeper bowl with stable bowl chirality and unique helical columnar packing in the crystal as an enantiopure form. In contrast, the crystal packing of the racemate shows a unidirectional columnar structure, which resembles that of the pristine sumanene. Doping of nitrogen atoms into the periphery of the sumanene framework also leads to perturbations of the electronic structure as shown by a significant decrease of the lowest unoccupied molecular orbital (LUMO) level and the optical band gap in comparison to all-carbon sumanene. The pyridine ring of triazasumanene shows unusual susceptibility towards acidic hydrolysis due to the highly strained curved structure.

    Although buckybowls have attracted considerable attention because of their bowl structures, still few heteroatom-doped buckybowls have been reported to date. Here we show the synthesis of triazasumanene having a deeper bowl with stable bowl chirality than sumanene. Nitrogen atoms on the periphery of the framework caused different crystal packing, electronic structure and reactivity towards acidic hydrolysis from those of sumanene. Fullsize Image
     
90th Commemorative Paper: Self-Organization
  • Junpei Sasaki, Masahiro Suzuki, Kenji Hanabusa
    2018 年 91 巻 4 号 p. 538-547
    発行日: 2018/04/15
    公開日: 2018/04/15
    ジャーナル 認証あり

    Supramolecular fluorescent gelators containing a tris(β-diketonato) complex are synthesized by using gelation-driving chelates, and their gelation abilities are studied with 15 solvents. Thin-layer films are prepared on quartz plates from the solutions and they are studied as chemosensors for amines. Fluorescence-quenching of the thin-layer films upon exposure to saturated primary and secondary amine vapors is monitored to evaluate the abilities of the chemosensors to detect amines. The morphologies of the thin-layer films are observed by transmission electron microscopy (TEM) and discussed in relation to their fluorescence-quenching. The fluorescence-quenching efficiencies upon exposure to saturated primary and secondary amines depend on the basicity and bulkiness of the amines rather than the vapor pressure. The fluorescence-quenching is caused by decomposition of a complex through nucleophilic addition of primary or secondary amines to its carbonyl group. The detection of tertiary amines is performed by monitoring the fluorescence emission from the thin-layer films, which are composed of a ligand and EuCl3. The emergence of fluorescence originates from the formation of fluorescent Eu3+-containing gelator, in which dehydrochloric acid by tertiary amines is a trigger for the complexation.

    Fluorescent gelators containing a tris(β-diketonato) complex are synthesized by using gelation-driving chelates, and their gelation abilities are studied. Thin-layer films are prepared on quartz plates from the solutions and studied as chemosensors for amines. The fluorescence-quenching efficiencies upon exposure to saturated primary and secondary amines depend on the basicity and bulkiness of the amines rather than the vapor pressure. Fullsize Image
     
 
  • Boyi Yang, Hongbin Liu, Rui Lv, Hui Li, Xin Fu, Jian Su, Xin Liu, Wen ...
    2018 年 91 巻 4 号 p. 548-553
    発行日: 2018/04/15
    公開日: 2018/04/15
    ジャーナル 認証あり

    A polyhedral Zn-based MOF [Zn (B-BDC) (Dpy)] •H2O (B-BDC = 3, 5-Dicarboxyphenylboronic acid, Dpy = 4, 4′-Bipyridine) (CCDC: 1559247), named Zn-BDC, has been initially designed and constructed via hydrothermal method. Then, its crystal structure, morphology and thermal properties were confirmed by using a series of characterization methods. Furthermore, composite materials, denoted as Zn-BDC-T (T = pyrolysis temperature), were synthesized by directly calcining Zn-BDC under N2 atmosphere at different temperatures. Herein, Zn-BDC-800 was recognized as N-doped Zn3B2O6 composite according to characterization results. When the Zn-BDC-800 was used as electrode materials for sodium-ion batteries, it exhibited a maximum discharge specific capacity of 295.6 mAhg−1 at the current density of 50 mAg−1 and its coulombic efficiency still remained at 99% after 100 cycles. Thus, this N-doped Zn3B2O6 polyhedral composite derived from Zn-MOF has broad development prospects in the field of SIBs.

Award Account
Lectureship Award in Asian International Symposium for 2017
  • Lei Mei, Wei-qun Shi, Zhi-fang Chai
    2018 年 91 巻 4 号 p. 554-562
    発行日: 2018/04/15
    公開日: 2018/04/15
    ジャーナル 認証あり

    Entangled structures in actinide-organic hybrid materials featured by intertwining between isolated motifs show promising potential in the application of different fields, such as radionuclide separation, radiation detection, photocatalysis and smart materials. Since how the individual motifs are entangled in combination of molecular structures of the structural units and topology of the individual motifs contributes most to the properties of actinide entangled materials, it is of significance to summarize and analyze these entanglements with diverse topologies. For this contribution, we will summarize all the entanglements in the reported actinide-organic entangled structures by classifying them according to the diverse catalogues of individual motifs and entangled patterns between them, among which are included all these intriguing types of entanglement in different seperate sections: 1) polyrotaxanes; 2) parallel interpenetration (INT) and polycatenation (P-CAT and I-CAT); and 3) Borromean ring (BR). This work is aimed at figuring out some clues on design principles of actinide-organic entangled structures, the underlying rules of ordered entanglement and driving forces behind from our perspective so as to provide some valuable principles guiding the assembly process of entangled structures for reference and help to achieve the controlled syntheses of actinide compounds of interest in the future.

    For this contribution, we will summarize the classification in the reported actinide-organic entangled structures by classifying them according to the diverse catalogues of individual motifs and entangled patterns between them, among which are included all these intriguing types of entanglement in different seperate sections: 1) polyrotaxanes; 2) parallel interpenetration (INT) and polycatenation (P-CAT and I-CAT); and 3) Borromean ring (BR). Fullsize Image
     
 
90th Commemorative Paper: Self-Organization
  • Eduardo Ruiz-Hitzky, Almudena Gómez-Avilés, Margarita Darder, Pilar Ar ...
    2018 年 91 巻 4 号 p. 608-616
    発行日: 2018/04/15
    公開日: 2018/04/15
    ジャーナル 認証あり

    Dimethylsila-14-crown-5 (DMS14C5) and dimethylsila-17-crown-6 (DMS17C6) macrocyclic polyethers have been intercalated into montmorillonite layered silicates containing Li+, Na+ or K+ cations as exchangeable cations. XRD and FTIR spectroscopy offer information on the disposition of the macrocycle in the interlayer and accommodation of cations within the cavity of the polyoxyethylene ligand. 13C and 23Na solid-state NMR spectroscopy provides information about the replacement of water molecules from the hydration shell of interlayer cations by the macrocyclic ligand and confirms differences in the interactions depending on the nature of the ligand. The resulting montmorillonite intercalation materials were tested as active phase of PVC electrodes for the development of potentiometric sensors, in a preliminary attempt to evaluate their electrochemical response towards alkali-metal ions in solution.

    New supramolecular materials are prepared by intercalation of two macrocyclic silacrown ethers into montmorillonite layered silicate. The resulting hybrid materials were characterized by diverse physicochemical techniques and tested as active phase of PVC electrodes for the development of potentiometric sensors, evaluating their electrochemical response towards alkali-metal ions in solution. Fullsize Image
     
 
90th Commemorative Account: Self-Organization
  • Toshimi Shimizu
    2018 年 91 巻 4 号 p. 623-668
    発行日: 2018/04/15
    公開日: 2018/04/15
    ジャーナル 認証あり

    Not only amphiphiles but also non-amphiphilic or π–conjugated molecules, if rationally designed, have been found to self-assemble in liquid media to form discrete tubular architectures with well-defined dimensions. This review covers most of the molecular building blocks that spontaneously produce organic nanotubes (ONTs) through self-assembly. Starting with the comparison of synthetic procedures and physical properties between the ONTs and carbon nanotubes (CNTs), the author discusses the classification of formation mechanism for the self-assembled ONTs. Then, membrane- or sheet-based, nanoring- or nanotoroid-based, stacking-based, and supramolecular stacking-based pathways of the self-assembly are described in relation to the presence or absence of intermediate structures. Concerning the membrane- or sheet-based mechanism, the molecular design and functionalities of each building block, and the dimensions of obtained ONTs are discussed in terms of the self-assembling features of amino acids, bile acids, carbohydrates, nucleotides, photoresponsive amphiphiles, functional dyes, fused aromatics, carbon allotropes, heterocycles, peptide derivatives, and other related molecules. Naphthalenediimide, porphyrins, and azobenzene amphiphiles are introduced to feature the ONT formation mediated by nanoring or nanotoroid structures. Cyclic peptides, polymer cyclic peptides, and peptide helices are then described as building blocks that result in the stacking-based self-assembly of the ONTs. Trimesic acids, pyrimido pyrimidine, ferrocene aromatics, and bent-shaped or cyclic aromatic amphiphiles are also discussed from the viewpoint of supramolecular stacking into the ONTs. Finally, currently important but critical issues for further development of the ONTs toward practical applications are described.

    This review article covers recent advances from 2010 on, regarding the molecular self-assembly into discrete closed hollow structures (organic nanotubes) from molecular building blocks. Starting with the comparison of synthetic procedures and physical properties between the ONTs and carbon nanotubes (CNTs), the author discusses the detailed features in line with the classification for the formation mechanism of self-assembled ONTs; membrane or sheet-based, nanoring- or nanotoroid-based, stacking-based, and supramolecular stacking-based pathways. Fullsize Image
     
 
  • Katsunori Iwase, Yasuhiro Toyama, Isao Yoshikawa, Yasuhisa Yamamura, K ...
    2018 年 91 巻 4 号 p. 669-677
    発行日: 2018/04/15
    公開日: 2018/04/15
    ジャーナル 認証あり

    To elucidate the relationship between prototropic tautomerism and the cold crystallization phenomenon, o-hydroxy aryl Schiff base compounds derived from three different toluidine isomers were examined. Comparing their thermal behavior, we confirmed that cold crystallization occurred to give a different crystalline phase compared to the initial state. To elucidate the mechanisms of the cold crystallization of the materials, their thermal, structural, and energetic properties were investigated. The DFT calculation of the molecules in their OH- and NH-forms suggested that the NH-form has higher molecular flexibility, which may prevent normal crystallization upon cooling, compared to the OH-form. Spectroscopic analyses implied that the molecules are present as a mixture of the OH- and NH-forms, and that they efficiently crystallize when a preferable OH/NH ratio is achieved. For this molecular system, we concluded that the equilibrium between NH- and OH-forms controls the supercooling of the liquid as well as nucleation and crystal growth.

  • Yuki Takeuchi, Tatsuhiro Asano, Kazuya Tsuzaki, Koichi Wada
    2018 年 91 巻 4 号 p. 678-683
    発行日: 2018/04/15
    公開日: 2018/04/15
    ジャーナル 認証あり

    The asymmetric amination of epoxides is an effective method to synthesize chiral β-aminoalcohols and their components as pharmaceuticals. We have developed a new catalyst system for the asymmetric amination of 1,2-epoxycyclohexane with cyclopropylamine. We have also found that water-soluble soy polysaccharide (Soyafibe S-DN) functions as a catalyst. This catalytic reaction proceeded under mild conditions in hydrous toluene at 37–40 °C. (1R,2R)-2-(cyclopropylamino)cyclohexan-1-ol was obtained at 64% enantiomeric excess (ee) by the asymmetric amination of 1,2-epoxycyclohexane with cyclopropylamine using this catalyst system; it was also made at >99% ee by purification as the fumarate salt. The catalytic activity of this soluble soy polysaccharide remained unchanged, even when treated with a protease, but its activity disappeared when treated with a sugar chain degrading enzyme. These results indicate that the polysaccharide rather than the protein acts as the catalyst for this reaction. Thus, we have discovered for the first time that polysaccharides can act as asymmetric catalysts for the amination of 1,2-epoxycyclohexane.

  • Takashi Abe, Shintaro Ishida, Takeaki Iwamoto
    2018 年 91 巻 4 号 p. 684-686
    発行日: 2018/04/15
    公開日: 2018/04/15
    ジャーナル 認証あり

    Dialkyl(potassio)silyl radical 6a[K(18-crown-6)] and dialkylsilylene radical anion 6b[K([2.2.2]cryptand)] were synthesized by the one-electron reduction of dialkylsilylene 5 and characterized by X-ray diffractional analysis and EPR spectroscopy. The structural change from 5 to 6b upon the one-electron reduction can be explained by reduced σ(Si–C) → 3p(Siα) orbital interactions.

90th Commemorative Account: Self-Organization
  • Shikha Dhiman, Subi J. George
    2018 年 91 巻 4 号 p. 687-699
    発行日: 2018/04/15
    公開日: 2018/04/15
    ジャーナル 認証あり

    The urge towards a precise control over structure and function of supramolecular polymers has recently aroused interest in temporally controlled supramolecular polymerization. The field is divided into two; living and transient supramolecular polymerization. The former deals with structural control such as length and dispersity, analogous to living polymerization in conventional polymers. The latter requires a temporally controlled switching of a structural/functional state in a supramolecular polymer. Such a control has been inspired by nature that has a precise control over spatial and temporal regimes. In this account, we describe the necessity and challenges in achieving temporal control over supramolecular polymerization. We have reviewed important reports that have attempted to obtain living and transient supramolecular polymerization. Although there has been significant advancement, the field is still in infancy due to lack of generalized schemes and designs, and we have thus discussed our perspective towards the future directions to obtain general design and next level complex supramolecular materials with spatio-temporal control.

    Recent interests towards living and transient supramolecular polymerization has uncovered the facet of temporal control in supramolecular polymers. To achieve temporal control, understanding of energy landscapes of supramolecular polymerization is important to build new and generalized strategies. Fullsize Image
     
 
90th Commemorative Account: Fascinating Molecules and Reactions
  • Bin Wang, Henry N. C. Wong
    2018 年 91 巻 4 号 p. 710-719
    発行日: 2018/04/15
    公開日: 2018/04/15
    ジャーナル 認証あり

    Significant advances in the development of CDC reactions have been made in recent years. However, metal-free CDC reaction remains comparatively under-developed. In view that a variety of readily available, cheap and environmentally friendly bromine reagents have been employed in bromination or oxidation in organic synthesis, we would like to summarize and discuss in this review examples of bromine-mediated CDC reactions, delineating significant and promising applications of these reagents in metal-free functionalization of C-H bonds.

    A variety of readily available, cheap and environmentally friendly bromine reagents have been used for bromination or oxidation in organic synthesis. This review is a summary of bromine-mediated Cross-Dehydrogenative Coupling (CDC) reactions, showing promising future applications in metal-free functionalization of C-H bonds. Fullsize Image
     
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