Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 56 , Issue 2
Showing 1-50 articles out of 67 articles from the selected issue
  • Susumu Matsuzaki, Toshiharu Moriyama, Mitsukazu Onomichi, Koichi Toyod ...
    1983 Volume 56 Issue 2 Pages 369-374
    Published: 1983
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Charge transfer salts of tetrathiafulvalen (TTF) with five substituted p-benzoquinones (fluoranil, chloranil, bromanil, iodanil, and 2,3-dichloro-5,6-dicyano-p-benzoquinone) were prepared by diffusion and cooling methods. IR, Raman, and electronic spectra of these salts measured at room temperature showed that all except fluoranil salt formed two crystal phases, i.e., the diffusion and the cooling methods gave a mixed-valent and a monovalent ionic phases respectively. The degrees of charge transfer (ρ) of the mixed-valent salts were estimated from the Raman frequencies of ag ν3 of TTF, and nearly equal values (ca. 0.7) were obtained for all of them.
  • Shigeyuki Yokoyama, Tetsuya Oida, Seiichi Uesugi, Morio Ikehara, Tatsu ...
    1983 Volume 56 Issue 2 Pages 375-378
    Published: 1983
    Released: June 27, 2006
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    The advanced method of NMR lanthanoid-probe analyses was used for studying the molecular conformations of 8,2′-anhydro-8-thio-9-β-D-arabinofuranosyladenine (8,2′-S-cycloadenosine) 3′-monophosphate in aqueous solution. From the observed ratios of Pr(III)-induced shifts, Gd(III)-enhanced relaxation rates as well as vicinal spin-coupling constants, the most probable values (and standard deviations) of the fractional populations of the local conformations for the C5′–C4′ bond, sugar ring, C3′–O3′ bond, and O3′–P bond and the internal rotation angles of the two forms about the C3′–O3′ bond were determined by the program COFLEM. The internal rotation equilibrium about the C3′-O3′ bond was found to be interrelated with the puckering of the sugar ring. The advanced lanthanoid probe method is thus useful for the analyses of the conformational characteristics of cyclonucleotides as well as of unmodified nucleotides in aqueous solution.
  • Nobuyuki Ito, Tsunetake Fujiyama, Yasuo Udagawa
    1983 Volume 56 Issue 2 Pages 379-385
    Published: 1983
    Released: June 27, 2006
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    The concentration dependence of concentration fluctuations at 21, 32, and 42 °C and of Raman spectra at 21 °C were measured for binary solutions of 2-butoxyethanol (BE) and water. The existence of the two kinds of local structures is inferred; clathrate hydrate-like structure g[(H2O)50BE] and aggregate h[(H2O)4BE]. The compositions of these two structures are the same as those of the two phases into which the solution separates above the critical solution temperature. The phase separation is understood to be the end of the growth of the local structures, which already exist well below the critical solution temperature.
  • Kenjiro Meguro, Hiroshi Watanabe, Hiromu Kato, Kimihiko Ogihara, Kunio ...
    1983 Volume 56 Issue 2 Pages 386-388
    Published: 1983
    Released: June 27, 2006
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    Stable O/W type emulsions of perfluorocarbon such as perfluorodecalin (FDC) and perfluorotributylamine (FTBA) were prepared by using poly(oxyethylene)-poly(oxypropylene) block copolymer (Pluronic F-68) and sorbitan monolaurate (SL-10) as emulsifiers. The relationships between the behavior of “uptake and release” of oxygen into the emulsions and the factors responsible for a stable emulsion were studied. The initial rates of “uptake and release” of oxygen into the emulsions decreased with increasing the mean particle size, the concentration of emulsifiers, and the viscosities of the emulsions. On the other hand, the saturated amount of oxygen in the emulsions was independent on the mean particle size, but depended on the total amount of the perfluorocarbons in the emulsion.
  • Nobuo Shimo, Nobuaki Nakashima, Keitaro Yoshihara
    1983 Volume 56 Issue 2 Pages 389-391
    Published: 1983
    Released: June 27, 2006
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    Three transient absorption spectra in aqueous solution were observed by irradiation of benzene with an excimer laser (KrF, 248 nm or ArF, 193 nm). A short-lived absorption with a peak at 275 nm is assigned to the Sn←S1 absorption. A long-lived absorption, which appears as a clear shoulder at 230 nm, stays longer than 500 ns and is not shortened by oxygen. This species is tentatively assigned to benzvalene, and the quantum yield is determined to be ca. 0.1. Solvated electron with a peak at 720 nm was formed via multiphoton processes at a power level of 60 mJ/cm2 of an ArF laser. The Tn←T1 absorption was lower than our detection limit (ΦT<0.1).
  • Yukio Furukawa, Hideo Takeuchi, Issei Harada, Mitsuo Tasumi
    1983 Volume 56 Issue 2 Pages 392-399
    Published: 1983
    Released: June 27, 2006
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    Normal-coordinate analyses of s-trans-1,3-butadiene and its various deuterated and 13C-substituted analogs were performed using the group-coordinate force field, and a set of force constants was determined. The infrared spectra of the second stable conformer of 1,3-butadiene-d0, -1,1,4,4-d4, and -d6 were analyzed on the basis of normalcoordinate calculations of the planar s-cis form and a nonplanar gauche form. Such an analysis suggests that the second stable conformer takes a gauche form rather than the s-cis. To increase the number of reliable data to be used in this study, the infrared and Raman spectra of the d0, 1,1,4,4-d4, and d6 species were observed in low-temperature Ar matrices. The infrared spectra of the second stable conformer were also observed using a combination of the high-temperature nozzle and low-temperature matrix techniques.
  • Seiichi Miyajima, Nobuo Nakamura, Hideaki Chihara
    1983 Volume 56 Issue 2 Pages 400-404
    Published: 1983
    Released: June 27, 2006
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    A Geometrical model is presented which rationalizes the viscosity and self-diffusion coefficients and their anisotrcpies in nematic liquid crystals. The model is an extension of Eyring’s theory of the liquid state to the anisotropic fluid, based on the geometry of the constituent molecule. A novel concept, effective anisotropy factor of a molecule, is introduced which is determined from the viscosity coefficients. An empirical law on the principal viscosity coefficients by Kneppe et al. is given its molecular basis by this model. Self-diffusion coefficient tensor calculated from the available viscosity data of PAA, MBBA, and HBAB agree well with experiment.
  • Chizuko Tanaka, Jiro Tanaka, Karlheinz Dietz, Chuji Katayama, Masashi ...
    1983 Volume 56 Issue 2 Pages 405-411
    Published: 1983
    Released: June 27, 2006
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    The single crystal of dimethyldibenzotetrathiafulvalenium tetrafluoroborate (1 : 1) has been prepared by electrocrystallization. The crystal structure has been determined by X-ray crystal analysis. The salt crystallizes in Ibam with a=14.637(3), b=17.625(6), c=13.614(3) Å. The radical cations align along the c axis at nearly equal spacing forming eclipsed dimers and the dimeric units are stacked with a staggered mode. The electronic spectra of the radical cation and the dimer have been measured in solution and the assignment has been presented with an aid of the MO calculation by Pariser-Parr-Pople method. A charge transfer (CT) band observed in the dimer has been correlated with the charge resonance of unpaired electron between the HOMOs of the radical cations. Polarized reflection spectra of single crystal have been measured with three different crystal planes and the assignment of both the CT and molecular type bands have been confirmed with polarization measurement. The energy and the intensity of the CT band indicate that the unpaired electron is localized on each radical, but the CT configuration is involved significantly. The crystal is an insulator as is expected from the electronic structure; the large U, which is evidenced by the energy of the CT band, and the staggered packing hinders electronic conduction. It implies that a monovalent radical salt is difficult to be metallic unless a mixed valence state is involved.
  • Shigezo Shimokawa, Eiji Yamada, Kazuo Makino
    1983 Volume 56 Issue 2 Pages 412-415
    Published: 1983
    Released: June 27, 2006
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    A simple pressurized, externally heated, high-temperature proton NMR apparatus for the temperature range from 293 to 823 K and pressure range from 0.1 to 40 MPa is reported. The sample cell has a capillary opening and the vessel is pressurized by inert gas. An application of this apparatus to the thermal degradation of poly(vinyl chloride) is presented.
  • Shigeo Kondo, Yoshinori Koga, Taisuke Nakanaga, Shinnosuke Saëki
    1983 Volume 56 Issue 2 Pages 416-421
    Published: 1983
    Released: June 27, 2006
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    The integrated intensities of the fundamental bands of CH3Cl and CD3Cl molecules have been measured by the pressure broadening technique. The Coriolis intensity perturbation between ν3 and ν6 bands of CD3Cl has been analysed to determine the sign to be negative. The intensity analysis has been carried out to determine the correct signs of (∂p/∂Qi). The resulting signs are (−++) for A1 and (−+−) for E species. The (∂p/∂SjR) values as well as the atomic polar tensors have been obtained.
  • Keiichiro Hatano, Kazunori Anzai, Yoichi Iitaka
    1983 Volume 56 Issue 2 Pages 422-427
    Published: 1983
    Released: June 27, 2006
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    Bis(methanol)-α,β,γ,δ-tetraphenylporphinatomanganese(III) perchlorate crystallizes as the methanol solvate in the triclinic system, space group P\bar1, a=16.225(8), b=13.167(7), c=10.793(5) Å, α=106.51(5)°, β=100.36(5)°, γ=101.60(5)°, and Z=2. The structure was determined by the heavy-atom method and the block-diagonal least-squares refinement using a total of 9992 reflections. The final R and Rw values are 6.3 and 7.1%, respectively. Two slightly different but substantially identical coordination spheres of high-spin Mn(III) porphyrin were revealed. The long axial Mn–O(methanol) bond distance and medium-sized porphyrin core were emphasized as structural characteristics in relation to the intermediate-spin iron(III) porphyrin.
  • Osami Abe, Taizo Utsunomiya, Yoshio Hoshino
    1983 Volume 56 Issue 2 Pages 428-433
    Published: 1983
    Released: June 27, 2006
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    The reaction of sodium nitrite with silica has been investigated over the relatively wide composition range (Na/Si=0 to 10.0) below 800 °C. In an argon atmosphere, sodium nitrite reacts with oxygen to form sodium nitrate above 400 °C and decomposes to sodium oxide via other oxide species above 500 °C, irrespective of the coexistence of silica. The reaction of sodium nitrite with silica in an argon atmosphere consists of two stages. In the early stage (<600 °C), the main gaseous product is NO, while in the later stage nearly equimolar amounts of NO and O2 are formed. The early stage is further divided into two reaction processes: Process I, in which peroxide is considered to be formed in the melt by generating NO, and Process II, in which nitrate and silicates are formed by generating NO and a trace amount of O2. Peroxide is supposed to be stabilized at the solid-liquid interface, even if no silicates have been formed at relatively low temperatures. In the later stage, the reaction process or mechanism can be regarded as similar to that of sodium nitrate with silica, as the concentration of nitrite in the melt is very low.
  • Yasuo Iwata, Hiroki Haraguchi, Jon C. Van Loon, Keiichiro Fuwa
    1983 Volume 56 Issue 2 Pages 434-438
    Published: 1983
    Released: June 27, 2006
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    The identification of rock-forming and clay minerals contained in the reference material of “Pond Sediment” (Reference Material NIES No. 2 from the National Institute for Environmental Studies, Japan) has been made with X-ray diffraction method. It was found that the sediment contained α-quartz and feldspars as the principal components along with small quantity of pyroxenes, amphiboles, and some clay minerals. The sediment sample was treated chemically for extraction, and also separated with density and with grain sizes. Elemental compositions of such extracted or separated fractions of the sediment were determined by inductively coupled argon plasma emission and atomic absorption spectrometry. The identified minerals and the elemental distributions in the separated fractions helped to characterize the pond sediment.
  • Tetsuaki Nishida, Yoshiaki Miyamoto, Yoshimasa Takashima
    1983 Volume 56 Issue 2 Pages 439-442
    Published: 1983
    Released: June 27, 2006
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    A linear decrease in isomer shifts of Fe3+ and Fe2+ was observed with an increase in alkali content of borophosphate glasses. The decrease is attributed to a change in the role of iron from a network modifier to a network former, or a decrease in the interatomic distance between iron and oxygen atoms. A linear decrease in quadrupole splitting and linewidth was also observed with increasing alkali content, and the decrease is attributed to the increased symmetry around iron nucleus. A linear decrease in relative absorption area of Fe2+ in Mössbauer spectra was also observed with increasing alkali content of the glasses. This result is attributed to an increased oxidation atmosphere brought about by alkali oxide into BPO4 units. Gamma-ray irradiation (1×108 R) experiments resulted in no change in these Mössbauer parameters, indicating that the glasses are less sensitive to γ-rays than borate or phosphate glasses. ESR absorption intensity of PO42− observed in γ-ray irradiated, iron-free borophosphate glasses increased linearly with an increase in the alkali content in the lower alkali region, and the increase is attributed to a linear increase in the fraction of non-bridging oxygen in PO4 tetrahedra constituting BPO4 (and PO4) units.
  • Hyo-Gwang Lee, Yukiei Matsumoto, Toshio Yamaguchi, Hitoshi Ohtaki
    1983 Volume 56 Issue 2 Pages 443-448
    Published: 1983
    Released: June 27, 2006
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    The structure of hydrated oxonium ion has been determined in a concentrated hydrochloric acid solution by the X-ray diffraction method. The oxonium ion H3O+ combines with four water molecules to form a trigonal pyramid structure in which three water molecules have an H3O+–H2O distance of 2.44 Å, while the water molecule at the apex of the pyramid is separated by 2.90 Å from the central oxygen atom of the oxonium ion. The structure of the CoCl+ determined in a relatively dilute lithium chloride solution (the Cl/Co mole ratio is 3.38) shows that the cobalt(II) ion is coordinated with five water molecules, the Co–OH2 distance being 2.14 Å. The Co–Cl distance within the complex is 2.35 Å. The CoCl42− complex has a regular tetrahedral structure both in a concentrated lithium chloride (Cl/Co=22.1) and a hydrochloric acid (Cl/Co=21.1) solutions with the Co–Cl bond length of 2.29 Å.
  • Reiko Saito, Yoshinori Kidani
    1983 Volume 56 Issue 2 Pages 449-454
    Published: 1983
    Released: June 27, 2006
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    Optically active (1R,2S)-1-aminomethyl-2-methylcyclohexylamine (R,S-2m-amcha) was synthesized and two Pt(II) and two types of Co(III) complexes containing this ligand were prepared. 1H-NMR and 13C-NMR spectra of the Pt(II) complexes and CD spectrum of trans-[CoCl2(R,S-2m-amcha)2]+ indicated that the chelate ring takes predominantly the λ conformation with the equatorial C1–C2 bond of the cyclohexane ring. The absolute configuration of the ligand has been assigned on the basis of the conformation of the complexes. All possible isomers of the tris Co(III) complex, fac-Δ(lel3), mer-Δ(lel3), mer-Λ(ob3), and fac-Λ(ob3), were isolated and characterized.
  • Nobuatsu Watanabe, Tsuyoshi Nakajima, Masayuki Kawaguchi, Akira Izumi
    1983 Volume 56 Issue 2 Pages 455-457
    Published: 1983
    Released: June 27, 2006
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    Poly(dicarbon monofluoride), (C2F)n is prepared with a higher reaction rate via the graphite interca lation compound formed through a reaction with F2 and AlF3 than from exfoliated graphite itself. The former process also has the advantage of including the formation of exfoliated graphite by the decomposition of an intercalation compound and its fluorination. The graphite fluoride thus prepared contained (C2F)n by 60–78%. The reaction time required for completing the reaction did not give a linear relationship, but a minimum point around 267×102 Pa against the fluorine pressure and there was almost no increase above 667×102 Pa of fluorine. However, the F/C ratios of graphite fluoride had, inversely, a maximum point against the fluorine pressure, indicating that the (C2F)n content in graphite fluoride was approximately proportional to the reaction time.
  • Makoto Watanabe, Toshihiko Inagaki, Shoji Sato
    1983 Volume 56 Issue 2 Pages 458-462
    Published: 1983
    Released: June 27, 2006
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    Calcium bis(hydrogenphosphoramidate)–water (2/3) was made by adding an aqueous calcium chloride solution to an aqueous potassium hydrogenphosphoramidate solution. The product decomposed slowly to diammonium calcium diphosphate monohydrate in air at room temperature. When the product was heated above 600 °C, the decomposition product was β-type calcium metaphosphate. According to the result of the isothermal decomposition of the product at 150 °C in air, no formation of P–NH–P linkages by the elimination of NH3 from P–NH2 linkages was observed, and it was concluded that the phosphoramidate thermally decomposed to form only polyphosphates in air.
  • Toshiro Yokoyama, Atsushi Kikuchi, Tetsuo Kimura, Toshishige M. Suzuki
    1983 Volume 56 Issue 2 Pages 463-466
    Published: 1983
    Released: June 27, 2006
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    Bidentate and tridentate ligands, 2-pyridylmethylamine, N-[2-(2-pyridyl)ethyl]ethylenediamine, salicylamine, and 2-thenylamine are incorporated into polystyrene–2%-divinylbenzene copolymer beads. These chelating resins are evaluated for their chelation capacity toward transition metal ions (Co2+, Ni2+, Cu2+, and Zn2+) at various pH. The chelating resins containing pyridine derivatives show a high capacity and selectivity. The selectivity of the resins for the metal ions is in the order, Cu2+>>Ni2+>Co2+≥Zn2+ which is in accord with the order of the formation constants of the introduced ligands. Separation of a metal ion mixture (Cu2+, Ni2+, Zn2+) into its components is undertaken by a column containing the chelating resin derived from N-[2-(2-pyridyl)ethyl]ethylenediamine. The present resins can also be used for the elimination of trace amount of harmful heavy metal ions such as Hg2+ and CrO42−.
  • Yasuo Abe, Hideo Horii, Setsuo Taniguchi, Kazuo Kamai, Masanosuke Taka ...
    1983 Volume 56 Issue 2 Pages 467-470
    Published: 1983
    Released: June 27, 2006
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    The autoxidation of 2,3-dihydroxy-2-propenal (triose reductone) was investigated between pH 2.83 and 13.91 in the presence of disodium dihydrogen ethylenediaminetetraacetate (EDTA 2NA). The reaction obeyed the first-order rate law with respect to the triose reductone and the zeroth-order rate law with respect to oxygen when the oxygen concentration was higher than 0.246 mM (1 mM=10−3 mol dm−3) at 30 °C. The pH dependence of the reaction rates showed that the reaction rates are governed by the acid-base equilibrium of triose reductone. The rate constants for neutral and singly- and doubly-charged anions of triose reductone at 30 °C were (3.6±0.1)×10−6, (7±1)×10−5, and (1.8±0.1)×10−2 s−1 respectively. The hydrogen peroxide produced as a result of the triose reductone oxidation was also found to oxidize triose reductone.
  • Makoto Kimura, Yoshiro Ogata
    1983 Volume 56 Issue 2 Pages 471-473
    Published: 1983
    Released: June 27, 2006
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    Photochemical oxidation of aromatic sulfonic acids such as p-cumenesulfonic, 2-mesitylenesulfonic, 1- and 2-naphthalenesulfonic acids with aqueous sodium hypochlorite has been studied. Addition of a large excess of alkali enhances the decomposition of sulfonic acids remarkably. p-Cumenesulfonic and 2-mesitylenesulfonic acids are oxidized faster than 1- and 2-naphthalenesulfonic acids. The photooxidation of sulfonic acids with an equimolar amount of hypochlorite gives intermediary oxidation products involving desulfonation to parent hydrocarbons, aromatic hydroxylation, side-chain oxidation, and ring cleavage; e.g., p-cumenesulfonic acid gives cumene, 2- and 4-isopropylphenol and 2-phenyl-2-propanol; 1- and 2-naphthalenesulfonic acids give phthalic anhydride. Light-absorbing aromatic sulfonic acids sensitize the decomposition of hypochlorite ion leading to hydroxyl radical, which reacts mainly with ground state sulfonic acid to give radical intermediates. The photooxidation may also involve direct C–S bond fission of sulfonic acids.
  • Hiroshi Nishino, Kazu Kurosawa
    1983 Volume 56 Issue 2 Pages 474-480
    Published: 1983
    Released: June 27, 2006
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    Seven 9-xanthenones were oxidized with manganese(III) acetate to give carboxy-, dicarboxy-, (acetoxymethyl)(carboxy)-, (carboxy)(hydroxymethyl)-, and acetoxymethyl-9-xanthenones, and to yield small amounts of (carboxymethyl)(carboxy)-, carboxymethyl-, (acetoxymethyl)(carboxymethyl)-, bis(acetoxymethyl)-, and diacetoxymethyl-9-xanthenones. The carboxyl group was preferentially introduced into the peri positions and the acetoxymethyl groups were located at positions ortho to the methoxyl or methyl group. The regioselectivity and mechanism of the carboxylation reaction is discussed briefly.
  • Kousuke Kusuda
    1983 Volume 56 Issue 2 Pages 481-486
    Published: 1983
    Released: June 27, 2006
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    Treatment of decachloro(4-allylidenecyclopentene) with enneacarbonyldiiron(0) gave octachlorobicyclo[3.3.0]octa-1,3,7-triene (δ-C8Cl8) in 40% yield. Dechlorination of decachlorobicyclo[3.3.0]octa-2,6-diene with powdered selenium, sulfur, phosphorus, or titanium in the presence of anhydrous aluminium chloride without any added solvent at 90–100 °C afforded octachlorobicyclo[3.3.0]octa-1,4,6-triene (2) (ε-C8Cl8) in good yield. Hexachlorobicyclo[3.3.0]octa-3,5,8-trien-2-one obtained from 2 was chlorinated by a concentrated solution of antimony(V) chloride in refluxing dichloromethane to give octachlorobicyclo[3.3.0]octa-3,6(or 7)-dien-2-one, but in a dilute solution (less than 0.1 g of antimony(V) chloride/cm3 of dichloromethane) hexachlorobicyclo[3.3.0]octa-4,6,8-trien-2-one (14) was obtained. Mechanism of the isomerization is discussed in terms of antiaromaticity of cyclopentadienyl cation. Reaction of 14 with methanol afforded pentachloro-4-methoxybicyclo[3.3.0]octa-3,5,7-trien-2-one. Ethanol or 2-propanol reacted with 14 similarly giving pentachloro-4-ethoxybicyclo[3.3.0]octa-3,5,7-trien-2 -one or pentachloro-4-isopropoxybicyclo[3.3.0]octa-3,5,7-trien-2-one, respectively.
  • Tadatoshi Ota, Seizo Masuda, Hitoshi Tanaka, Yasuo Inazawa, Masaru Kid ...
    1983 Volume 56 Issue 2 Pages 487-490
    Published: 1983
    Released: June 27, 2006
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    The thermal oligomerization of methacrylaldehyde oxime leads to 2,4,7-trimethylperhydroisoxazolo[2,3-a]pyridine-2,7-dicarbaldehyde dioxime (1). The β-form of 1 was separated, and its crystal structure was determined by X-ray analysis. It is monoclinic with space group P21/c, a=13.274(11), b=8.652(7), c=11.618(14) Å, β=96.73(8)°, and Z=4. The molecules are linked by two N···O hydrogen bonds, with the N(13)···O(14) and N(8)···O(18) distance of 2.824(5) and 2.897(5) Å respectively.
  • Takashi Matsumoto, Shuji Usui
    1983 Volume 56 Issue 2 Pages 491-493
    Published: 1983
    Released: June 27, 2006
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    Oxidation of the synthetic pallescensin 1 with m-chloroperbenzoic acid, followed by treatment of the resulting epoxide with lithium diethylamide, afforded 3-[2-(2-furyl)ethyl]-4,4-dimethyl-2-methylenecyclohexanol (6). The alcohol 6 was dehydrated with refluxing hexamethylphosphoric triamide to give pallescensin 2. Oxidation of 6 with pyridinium chlorochromate, followed by intramolecular cyclization with 85% phosphoric acid, afforded 5,5a,6,7,8,9,9a,10-octahydro-6,6-dimethyl-4H-benzo[5,6]cyclohepta[1,2-b]furan-9-one. This was converted into the corresponding α,β-unsaturated ketone (10) via an α-phenylseleno ketone. Reduction of 10 with lithium aluminium hydride, followed by dehydration with hexamethylphosphoric triamide at 200–210 °C, afforded pallescensin G, which was further isomerized to pallescensin F.
  • Seiichiro Ogawa, Yasuhito Shibata, Noritaka Chida, Tetsuo Suami
    1983 Volume 56 Issue 2 Pages 494-498
    Published: 1983
    Released: June 27, 2006
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    β-D-Glucopyranosylvalidamine, the structure of which had first been assigned to a degradation product of validamycin A, was synthesized by condensation of a protected validamine with 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl bromide, followed by removal of protecting groups. The synthesized β-D-glucopyranoside was not identical with an authentic sample derived from the antibiotic.
  • Seiichiro Ogawa, Noritaka Chida, Hiroyuki Ito, Tetsuo Suami
    1983 Volume 56 Issue 2 Pages 499-504
    Published: 1983
    Released: June 27, 2006
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    The title β-D-glucopyranoside was synthesized via an unequivocal route and found to be identical with β-D-glucopyranosylvalidamine derived from antibiotic validamycin A. The position at which the validamine moiety is substituted with D-glucopyranose in validamycin A is revised to C-1 on the basis of the present synthesis.
  • Tatsushi Toyokuni, Yasuo Abe, Seiichiro Ogawa, Tetsuo Suami
    1983 Volume 56 Issue 2 Pages 505-513
    Published: 1983
    Released: June 27, 2006
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    Bromination of DL-tri-O-acetyl-(1,3/2)-4-methylene-5-cyclohexene-1,2,3-triol with bromine in an appropriate solvent yielded mainly two 1,4-addition products, from which several branched-chain unsaturated cyclitols, related to biologically interesting valienamine, were selectively prepared. Reaction courses are discussed for the bromination of the diene and the debromination of the bromo(bromomethyl)cyclohexenetriol triacetates obtained under various conditions.
  • Makoto Nitta, Akihiko Omata, Setsuko Hirayama, Yuji Yajima
    1983 Volume 56 Issue 2 Pages 514-519
    Published: 1983
    Released: June 27, 2006
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    The stereochemical course of the methoxymercuration-demercurations and the 1,3-dipolar cycloadditions of mesitonitrile oxide on the exocyclic double bonds of 2,4-dimethyl-7-methylenetetracyclo[3.3.0.0.2,804,6]octan-3-one (4a), its corresponding exo-3-ol (4b), endo-3-ol (4c), and 2,3,4-trimethyl-7-methylenetetracyclo[3.3.0.0.2,804,6]octan-3-exo-ol (4d) were investigated. In the methoxymercurations of 4a and 4b, the methoxyl group was incorporated in the exo and endo positions, with endo preferred over exo. On the other hand, 4c and 4d underwent the stereospecific incorporation of the methoxyl group in the endo position. In the 1,3-dipolar cycloadditions, 4a or 4b afforded exo- and endo-adducts, with the exo-adduct preferred. These results seem to imply similar stereochemical course of the formation of the mercurinium-ion intermediates and the 1,3-dipolar cycloadditions. The results are discussed on the basis of the steric hindrance of the molecular framework and the substituents which are located at the C-3 position.
  • Kiichiro Nakajima, Hitomi Oda, Kenji Okawa
    1983 Volume 56 Issue 2 Pages 520-522
    Published: 1983
    Released: June 27, 2006
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    A convenient synthesis of optically active S-alkylcysteine, threo-S-Alkyl-β-methylcysteine, and lanthionine derivatives has been investigated. Benzyl 1-benzyloxycarbonyl-(2S)-2-aziridinecarboxylate and benzyl (2S,3S)-1-benzyloxycarbonyl-3-methyl-2-aziridinecarboxylate, and their enantiomers were treated with several thiols, and the corresponding S-alkylcysteine, threo-S-alkyl-β-methylcysteine, and lanthionine derivatives were prepared via the ring-opening reaction of aziridine in the presence of a catalytic amount of boron trifluoride etherate in good yields.
  • Masato Kodaka, Toru Shimizu, Masahiro Hatano
    1983 Volume 56 Issue 2 Pages 523-527
    Published: 1983
    Released: June 27, 2006
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    A linear peptide, N-t-butoxycarbonyl-S-acetamidomethyl-L-cysteinyl-D-leucyl-L-histidyl-S-acetamidomethyl-L-cysteinyl-D-leucyl-L-histidine methyl ester (1) was synthesized by the solid phase method. Subsequent cyclization by the azide method offered a cyclic peptide, cyclo-S-acetamidomethyl-L-cysteinyl-D-leucyl-L-histidyl-S-acetamidomethyl-L-cysteinyl-D-leucyl-L-histidyl (2). The circular dichroism (CD) and 1H NMR were observed for these peptides 1 and 2, in the absence and presence of metal cations, Zn(II), Ca(II), Mg(II). Spectral results for Zn(II) complexes indicated striking contrasts to those of Ca(II) and Mg(II) complexes. Thus, in H2O, the addition of Zn(II) caused CD spectral changes for both peptides, while Ca(II) and Mg(II) did not cause changes in any CD spectral region. In methanol, the additions of Zn(II) and Ca(II) caused CD changes, while the addition of Mg(II) did not cause any CD changes. The changes caused by adding Zn(II) were quite different from those by Ca(II), suggesting that Zn(II) is coordinated with the peptides in a mode different from that of Ca(II). 1H NMR data also suggested the different coordination mode between these two metal complexes in methanol.
  • Isamu Matsuda, Hisashi Okada, Yusuke Izumi
    1983 Volume 56 Issue 2 Pages 528-532
    Published: 1983
    Released: June 27, 2006
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    2-Substituted 2-alkenenitriles are obtained in the condensation reaction of carbonyl compounds with C,N-bis(trimethylsilyl)ketenimine in the presence of Lewis acid. The combination of tris(trimethylsilyl)ketenimine and aldehydes results in the high E-selective formation of 2-trimethylsilyl-2-alkenenitriles. Among some Lewis acids, magnesium bromide gives the best E-selectivity in the formation of 2-trimethylsilyl-2-undecenenitrile. Stereospecific protodesilylation of 2-trimethylsilyl-2-alkenenitriles in an aqueous methanol solution of potassium fluoride accomplishes a new route to (Z)-2-alkenenitriles from aldehydes.
  • Masato M. Ito, Yujiro Nomura, Yoshito Takeuchi, Shuji Tomoda
    1983 Volume 56 Issue 2 Pages 533-536
    Published: 1983
    Released: June 27, 2006
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    Photolysis of 4-alkyl-5-ammo-1-vinyl-4,5-dihydro-1H-1,2,3-triazoles gave not 3-alkylpyrroles, but unexpected 2-alkylpyrroles in 80–83% yields. 1-Vinylaziridines were assumed as a possible intermediate of this unusual pyrrole formation. In the photolysis of 7a-morpholino-1-styryl-3a,4,5,6,7,7a-hexahydro-1H-1,2,3-benzotriazole, however, nitrogen extrusion did not occur, but trans-cis isomerization took place.
  • Sadatoshi Akabori, Yoichi Habata, Yhoko Sakamoto, Masaru Sato, Seiji E ...
    1983 Volume 56 Issue 2 Pages 537-541
    Published: 1983
    Released: June 27, 2006
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    Polyoxaferrocenophanes were synthesized by a one-pot reaction of 1,1′-diacetoxyferrocene with dichloride. Crystalline 1 : 1 complexes of 3a with LiSCN, NaSCN, and KSCN were isolated. The 1H-NMR and Mössbauer spectra of these complexes suggest the possibility of a certain interaction between the iron atom of the ferrocene nuclei and complexed cation. The new type of ferrocenophane 3a extracts a thallium ion most effectively, the extractability of several metal ions being in this order; Tl+>Rb+>K+>Cs+>Na+.
  • Atsushi Sakurai, Yasuaki Okumura
    1983 Volume 56 Issue 2 Pages 542-544
    Published: 1983
    Released: June 27, 2006
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    A new flavonoid glycoside, taxillusin was isolated from Taxillus kaempferi (DC.) Danser and (2R,3R)-taxifolin 3-β-D-glucopyranoside 6″-gallate was assigned to this substance from studies on the hydrolysis products and from analyses of the 1H-NMR and carbon-13 NMR spectra.
  • Suketaka Ito, Yumo Tanaka, Akikazu Kakehi, Toshihiko Fukuyama, Nobuo O ...
    1983 Volume 56 Issue 2 Pages 545-548
    Published: 1983
    Released: June 27, 2006
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    3,5-Disubstituted 1-methyl-1H-1,2,4-triazoles and -pyrazoles were obtained in good to moderate yields by the reaction of N-methyl-N-(phenylsulfonyl)benzohydrazonoyl chloride with nitriles and with acetylenes in the presence of aluminum chloride. The triazoles were also formed by the reaction of acid chlorides with N-methyl-N-(phenylsulfonyl)benzamidrazone which was generated from the hydrazonoyl chloride and ammonia.
  • Hiroshi Yoshida, Masayuki Kawai, Chiseko Okimura, Nobuyuki Hirama, Osa ...
    1983 Volume 56 Issue 2 Pages 549-553
    Published: 1983
    Released: June 27, 2006
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    For comparison with known phosphodiesterases, the mode of action of phosphodiesterase-phosphomonoesterase from Fusarium moniliforme toward some key substrates was examined. The enzyme catalyzed the hydrolysis of either thymidine 3′-(4-nitrophenylphosphate) or thymidine 5′-(4-nitrophenylphosphate). The former substrate was hydrolyzed processively into thymidine, inorganic phosphate and 4-nitrophenol, whereas the latter was split into 4-nitrophenol and thymidine 5′-phosphate. The kinetic constants determined on the basis of 4-nitrophenol liberation were: Km=4.6 mmol dm−3 and kcat=115 s−1 for thymidine 3′-(4-nitrophenylphosphate); Km=0.46 mmol dm−3 and kcat=19.7 s−1 for thymidine 5′-(4-nitrophenylphosphate) at pH 5.3 and 37 °C. 4-Nitrophenyl phenylphosphonate was a good substrate for the enzyme showing kinetic constants Km=1.4 mmol dm−3 and kcat=360 s−1 at pH 5.3 and 37 °C. However, its chiral thio analogue, O-(4-nitrophenyl) phenylphosphonothioate, was hydrolyzed by the enzyme only very slowly in a stereo-nonspecific manner. The three phosphoryl groups in adenosine triphosphate was removed by the enzyme sequentially from the terminal position. These findings have made the uniqueness of Fusarium phosphodiesterase-phosphomonoesterase clearer.
  • Munetaka Akita, Hajime Yasuda, Kinya Nagasuna, Akira Nakamura
    1983 Volume 56 Issue 2 Pages 554-558
    Published: 1983
    Released: June 27, 2006
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    The catalyst systems which consist of MCl2(C5R5)2(M=Ti, Zr; R=H, CH3)/NaC10H8, i-C3H7MgBr, n-C4H9Li or LiAlH4 in 1 : 2 ratio were highly effective for the stereoselective isomerization of monosubstituted 1-alkenes to (E)-2-alkenes. Unconjugated dienes were converted to (E)- or (E,E)-dienes. The catalysis of (C5Me5)TiCl2/NaC10H8 was extremely high and resulted in the complete isomerization of 1-alkenes in >99% stereoselectivity within a short period. The use of the bulky C5Me5 ligand is essential to find out the excellent stereoselectivity. Systems, (C5H5)2TiCl2/NaC10H8 and (C5H5)2TiCl2/i-C3H7MgBr showed less selectivity and the catalysis of the corresponding zirconium systems was very poor irrespective of the reducing agents and substrates.
  • Seiji Shinkai, Hidefumi Kinda, Yoshikazu Araragi, Osamu Manabe
    1983 Volume 56 Issue 2 Pages 559-563
    Published: 1983
    Released: June 27, 2006
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    We have found that 1,10-diaza-4,7,13,16-tetraoxa-18-crown-6 with a carboxylate cap and a hydrophobic dodecanoyl group (1) acts as a new class of ion carrier for membrane transport. The rate of K+ transport across a chloroform liquid membrane was significantly affected by pH of the OUT aqueous phase: The rate decreased with increasing or decreasing pH, providing a maximum at around pH 5. The main species of 1 in the neutral pH region should be zwitterionic 1±, so that one may rationalize the pH-rate profile in terms of (i) “enforced ion release” due to protonation of the ring nitrogen and (ii) high lipophilic nature of zwitterionic 1±. The efficiency of 1 was further demonstrated by active K+ transport from the basic IN aqueous phase to the neutral OUT aqueous phase. Also, 1 was capable of carrying amino acids in the presence of alkaline earth metal cations. These results suggest that, being different from conventional anion-capped crown ethers, the aza crown ethers carrying the N-substituted carboxylate cap exhibit a new class of ionophore functions.
  • Atsuyoshi Ohno, Satoshi Ushida, Shinzaburo Oka
    1983 Volume 56 Issue 2 Pages 564-567
    Published: 1983
    Released: June 27, 2006
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    1,4-Dihydronicotinamide derivatives covalently bound to NH2 or SH group of proteins such as reduced keratin (RK), egg white albumin (EWA), and bovine serum albumin (BSA) have been synthesized and subjected to the reductions of α,α,α-trifluoroacetophenone derivatives. Chiral alcohol is obtained in the reaction with 1,4-dihydronicotinamide modified by the SH group of BSA.
  • Toshihisa Ueda, Morinobu Saito, Tetsuo Kato, Nobuo Izumiya
    1983 Volume 56 Issue 2 Pages 568-572
    Published: 1983
    Released: June 27, 2006
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    Several cyclic dipeptides were synthesized by refluxing methanolic solution of dipeptide methyl esters in high yield and purity. Cyclic dipeptides prepared by the Fischer method, the Nitecki method, and the present methanol-reflux method were compared with respect to yield and optical purity. The methanol-reflux method usually gave good results. High-performance liquid chromatography was effectively applied to detect racemization.
  • Seizi Kozuka, Shigeru Yamaguchi, Waichiro Tagaki
    1983 Volume 56 Issue 2 Pages 573-576
    Published: 1983
    Released: June 27, 2006
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    A kinetic study has been conducted on the reactions of (aryloxy)trimethylstannanes with methanesulfonyl chloride giving chlorotrimethylstannane and aryl methanesulfonates. The reaction was found to obey a second order kinetic equation. The solvent effect on the rate of the reaction appeared obscure although a small rate enhancement was observed in a polar solvent. Substituent effect of the aryloxyl group was found to be dependent on the solvent used while a clear isokinetic relationship was observed. A charge separated four-center transition state has been suggested for the reaction.
  • Tokiko Uchida, Masanori Ito, Kozo Kozawa
    1983 Volume 56 Issue 2 Pages 577-582
    Published: 1983
    Released: June 27, 2006
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    Three forms of crystals were obtained from mixed solutions of phenothiazine and SbCl5; the crystal structure of the monoclinic(I) modification was determined using 2827 reflections at room temperature. Crystal data: (C12H9NS)SbCl6, F.W.=533.7, monoclinic, a=16.253(3), b=14.334(1), c=15.786(3) Å, β=104.07(1)°, space group C2/c, Dm=2.00, Dx=1.99 g cm−3, Z=8, μ=25.73 cm−1 (Mo Kα). The structure was solved by the heavyatom method and refined by block-diagonal least-squares method to R=0.072. The crystal consists of phenothiazine cation radicals(PT) and hexachloroantimonate anions(SbCl6), and every ion exists as a monomer in the crystal. Each SbCl6 forms a distorted octahedron. The two C–S distances of PT are 1.705 and 1.711 Å, and the C–S–C angle is 103.9°. The dihedral angle between the two outer phenyl rings of PT is 176.5°. From the ESR measurements of a single crystal, three principal g-values were determined: g1=2.003, g2=2.007 and g3=2.008. The direction of g1 is normal to the molecular plane of PT. These facts suggest some π-delocalization in the central ring of PT. Absorption spectra polarized parallel to the molecular plane of PT are very similar to the poly crystalline reflection spectra of PT salts obtained by other authors, and there are no intense bands in the spectra polarized perpendicular to PT molecular plane over the wave number range 10 to 27×103 cm−1.
  • Ikuo Tokue, Masami Ikarashi, Sadachika Takizawa, Yoshio Ito
    1983 Volume 56 Issue 2 Pages 583-587
    Published: 1983
    Released: June 27, 2006
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    In the wavelength region of 200–600 nm, photoemissions from electronically excited H, CH, C2, and CS (only from thiophene and tetrahydrothiophene) were observed when furan, tetrahydrofuran, thiophene, and tetrahydrothiophene were excited by electron impact (0–70 eV). Hydrogen atoms (n=4) and CH(A2Δ) radicals were produced from these five-membered heterocycles via single collision excitations, while CS(A1Π) radicals from thiophene and tetrahydrothiophene were partly formed in secondary processes. The appearance potentials for the hydrogen Balmer β and the CH(A2Δ-X2Π) bands from these five-membered heterocycles are determined, and the dissociation processes forming H(n=4) and CH(A) are discussed.
  • Kenichi Mitsumori, Kenzo Hiraoka
    1983 Volume 56 Issue 2 Pages 588-591
    Published: 1983
    Released: June 27, 2006
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    The luminescence from reactions of N2(A3Σu+) with solid benzene, toluene, hexane, cyclohexane and those doped with biacetyl at 77 K has been investigated. For benzene, a broad band appeared in the range of 350–550 nm whose radiative lifetime was determined to be 2.5 s. This band was largely eliminated by addition of a small amount of biacetyl, indicating the participation of an intermediate excited state in solid benzene, i.e. triplet excitons. The emitter of the broad band was tentatively assigned to reaction products, possibly benzene isomers. For toluene, a strong appearance of benzyl radical emission was observed. With an addition of biacetyl, the elimination of benzyl emission and a strong growth of biacetyl phosphorescence were observed as for the benzene/biacetyl system. With an increase of biacetyl concentration, a remarkable red shift were observed for biacetyl phosphorescence, while no shift was observed for benzyl emission, indicating the difference of the solvent effect for these electronic transitions. No luminescence was observed for solid hexane and cyclohexane.
  • Masahiko Fukuda, Akio Tajiri, Masaji Oda, Masahiro Hatano
    1983 Volume 56 Issue 2 Pages 592-596
    Published: 1983
    Released: June 27, 2006
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    Assignment of the electronic absorption spectrum of 1,4 : 5,8-anthracenediquinone (1,4 : 5,8-ADQ) has been carried out with the aid of magnetic circular dichroism and LCAO MO SCF CI calculations including all valence electrons. The lowest energy absorption region of 1,4 : 5,8-ADQ has been revealed to be composed of the n-π* transition or transitions. The higher energy absorption region has been concluded to consist of four π-π* transitions, which are regarded as Lb, La, Ba, and Bb in the Platt’s notation for anthracene. The above assignment of 1,4 : 5,8-ADQ has been experimentally confirmed with its linear dichroism spectra in stretched polyethylene sheets and its circular dichroism spectra in the β-cyclodextrin solution. The relationship between the absorption spectra of 1,4 : 5,8-ADQ and 1,4-naphthoquinone has been discussed from the experimental and theoretical points of view.
  • Takumi Matsuda, Saburo Kashiramoto, Kiwamu Yamaoka
    1983 Volume 56 Issue 2 Pages 597-601
    Published: 1983
    Released: June 27, 2006
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    The interaction between actinomycin D (AMD) and native and heat-denatured DNA was studied spectrophotometrically at 25 °C. By applying the principal-component-analysis (PCA) method to the series of observed spectra, the number of light-absorbing components was determined. Two spectroscopically different species of bound AMD, i.e., AMD–DNA complexes, were formed when an aqueous AMD solution was titrated with either the native or the denatured DNA solution over a wide range of the nucleotide residue-to-AMD mixing ratios (P/D) between 0 and 30. The pure spectra of AMD bound to DNA were extracted in the P/D range 0–4 by the extended PCA method with an appropriate binding scheme. These bound-AMD spectra were affected by the DNA conformation but not by the addition of NaCl (1–500 mmol dm−3). The fractions of bound AMD were calculated as a function of P/D.
  • Hiroshi Maeda, Kaoru Saito, Shoichi Ikeda
    1983 Volume 56 Issue 2 Pages 602-606
    Published: 1983
    Released: June 27, 2006
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    The effects of polymer concentration on the reversible conversion between the intermolecular β-structure and the disordered state of poly(S-carboxymethyl-L-cysteine) were examined by means of circular dichroism at constant pHs in 20 mM NaClO4 solutions. The data were tentatively analyzed based on an assumed all-or-none model. A value of −1.1 kJ (−250 cal) per mole of residues was obtained for the standard free energy of association. It was suggested that the obtained results depended significantly on the molecular weight distribution of the used samples.
  • Chie Miyake, Yukio Hinatsu, Shosuke Imoto
    1983 Volume 56 Issue 2 Pages 607-613
    Published: 1983
    Released: June 27, 2006
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    Studies of magnetic susceptibility, χ, from 300 to 2 K on seventeen UCl4–amide complexes showed that six complexes had maxima in χ between 155 and 82 K. This unusual magnetic behavior occurred only with N-methyl or ethyl-substituted amide complexes. Infrared and chemical evidence indicates that these six complexes probably have dimeric structure, in which two U(IV) ions are bridged by the amide ligands. Assuming a dimer structure and a two-spin Heisenberg model with −2Jex of about 90 cm−1 for the dimer, the magnetic susceptibilities for the six complexes were calculated in good agreement with the experimental results in the temperature region of the maxima in χ.
  • Chie Miyake, Yukio Hinatsu, Shosuke Imoto
    1983 Volume 56 Issue 2 Pages 614-618
    Published: 1983
    Released: June 27, 2006
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    The magnetic susceptibilities of five cyclic amide (lactam)-addition complexes of uranium(IV) chloride were measured between room temperature and 2 K. Magnetic-exchange interaction was found only for N-methyl-substituted amide complexes, and a dimer structure was assumed for them on the basis of their chemical properties. Treating interdimer interaction with a molecular-field approximation, the magnetic susceptibilities were calculated to be in good agreement with the experimental results in the temperature region of the maxima in χA. The transmission of antiparallel spin coupling via the π orbitals of the bridging amide ligands is proposed to explain the strong intradim er superexchange interaction for the uranium(IV) chloride–amide complexes with the magneticsusceptibility maximum.
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