Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
56 巻 , 6 号
選択された号の論文の77件中1~50を表示しています
  • Katsuhiko Ueno, Mitsuhiko Sato, Norio Saito
    1983 年 56 巻 6 号 p. 1577-1580
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    The title compound, C15H16O9·2H2O, crystallizes in orthorhombic space group P212121 with a=7.082(2), b=34.789(5), c=6.867(2) Å, and Z=4. The structure was solved by direct method and refined by least-squares to a final R of 0.038 based on 1841 observed reflections measured on a four-circle diffractometer. The coumarin ring is approximately planar and the torsion angle around the glucosidic C–O bond is 13.5°; this is much smaller than the corresponding value in 8-glucosyloxy-7-hydroxycoumarin, and causes considerable intramolecular repulsion around the glucosidic linkage. The valence angle of the oxygen atom linking the coumarin and glucose moieties is quite large, 118.5°. The glucopyranose portion is in a C1 chair conformation. Glucosidation at the 7-hydroxyl group brings about considerable decrease of the resonance system of the 7-hydroxylated coumarin moiety. Such an effect seems to play an important role in the transglucosidation of dihydroxycoumarin glucosides.
  • Kazuhiko Kandori, Ayao Kitahara, Kijiro Kon-no
    1983 年 56 巻 6 号 p. 1581-1584
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    The dispersion stability of needlelike and octahedral iron(III) oxides of magnetic or nonmagnetic particles in 2-butanone was studied. Two kinds of copolymers of poly(vinyl acetate-vinyl chloride-maleic acid) (VAVCCOOH) and poly(vinyl acetate-vinyl chloride-vinyl alcohol) (VAVCOH) were used as dispersants. The sedimentation of dispersions, the adsorption of copolymer dispersants on the particles and zeta potentials were measured. By polymer adsorption, the dispersion of nonmagnetic needlelike iron(III) oxide was stabilized and the dispersions of magnetic needlelike iron(III) oxides were somewhat stabilized, but the dispersions of magnetic octahedral iron(III) oxides were only slightly stabilized. This characteristic behavior of the sedimentation experiment was discussed in relation to the amount of polymer adsorption and zeta potential and was correlated with the observations by an electron microscope. The magnetic attractive force operating between the two magnetic particles was calculated to illustrate the dispersibility of magnetic oxides. It was suggested from the calculation that the strength of the magnetization and the volume of a particle are the main factors affecting the flocculation of the magnetic particles.
  • Sadakatsu Nishikawa, Tatsuro Yamaguchi
    1983 年 56 巻 6 号 p. 1585-1587
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    Ultrasonic absorption and velocity measurements have been performed in aqueous solutions of Allyl Cellosolve (ethylene glycol monoallyl ether) as functions of the concentration and the temperature. Only a single relaxational absorption has been observed in the frequency range from 15 to 220 MHz and, it has been attributed to the perturbation of the equilibrium expressed as AB\ ightleftharpoonsA+B, where A and B are the solute and the solvent molecule respectively. The rate constants at various temperatures have been determined from the concentration dependence of the relaxation frequency, and the thermodynamic parameters associated with the reaction have been calculated. The enthalpy change has also been estimated from the concentration dependence of the maximum excess absorption per wavelength. From these results, it has been concluded that Allyl Cellosolve molecules act as water structure promoters and that the interaction between the solute and the solvent is due to hydrogen bonding. Furthermore, the rate and the thermodynamic properties obtained are compared with those for aqueous solutions of other ethers.
  • Noriyuki Mizoguchi
    1983 年 56 巻 6 号 p. 1588-1591
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    The imaginary bond-bond polarizability has been studied. Several general relations exist between the bond order and the imaginary bond-bond polarizability and between imaginary bond-bond polarizabilities.
  • Hiroyoshi Kanai, Yoshimasa Nishiguchi, Hideki Matsuda
    1983 年 56 巻 6 号 p. 1592-1597
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    The reaction of bis(acetonitrile)bis(diethyl fumarate)cobalt(0) with dibromomethane gave diethyl trans-1,2-cyclopropanedicarboxylate in a 67% yield based on the cobalt complex. Dimethyl cis-1,2-cyclopropanedicarboxylate was obtained in a 52% yield from the reaction of dimethyl maleate with dibromomethane in the presence of acetonitrilebis(dimethyl maleate)nickel(0) accompanied by the formation of the trans-isomer in a 14% yield. The addition of zinc gave cyclopropanes in over 100% yields based on cobalt or nickel. 3-Methyl- and 3,3-dimethyl-1,2-cyclopropanedicarboxylic acid esters were produced by the reaction of dimethyl fumarate or maleate with 1,1-dibromoethane and 2,2-dibromopropane. The yield in the cobalt catalyst system decreases with an increase of substituents of gem-dibromides, while that in the nickel catalyst system does not vary appreciably. A small amount of dimethyl isopropenylsuccinate was formed as a by-product in the reaction of 2,2-dibromopropane. A mechanism is briefly discussed which involves metallacyclobutane as an intermediate.
  • Yoshihumi Kusumoto, Gilbert R. Seely, Velu Senthilathipan
    1983 年 56 巻 6 号 p. 1598-1606
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    When chlorophyll, together with certain other amphiphilic substances, is adsorbed to particles of polyethylene plasticized by incorporation of tetradecane, it is maintained in monomeric or oligomeric forms with characteristic absorption and fluorescence spectra. The present work describes the properties of chlorophyll a on such particles in the presence of the three isomeric N-pyridylmyristamides, and of the similarly shaped but not basic compound myristanilide, in an effort to ascertain the structural factors governing associations of these species. Absorption and fluorescence spectra at room temperature are resolved into minimal sets of Gaussian components, and relations between the component sets are proposed. The positions of the component bands and their relative abundance are characteristic of the amide used. The 3- and 4-pyridyl isomers bind more strongly to chlorophyll, probably by ligation of the pyridine nitrogen to Mg of the pigment. The 2-pyridyl isomer and myristanilide bind more weakly, probably through the amide carbonyl group. The association of chlorophyll into species with characteristic absorption and fluorescence bands is promoted more strongly by the 3- and 4-isomers than by the 2-isomer and myristanilide, and probably involves hydrogen bonding to chlorophyll carbonyl groups. A possible manner of association of chlorophyll in the presence of N,N-dimethylmyristamide is also presented. By way of comparison, chlorophyll adsorbed with N-dodecylpyridinium bromide, which lacks a nucleophilic function, is mainly in the microcrystalline hydrate form absorbing near 740 nm.
  • Masayuki Nakagaki, Emiko Okamura
    1983 年 56 巻 6 号 p. 1607-1611
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    The surface pressure of the monolayers of dimyristoyl phosphatidylcholine (DMPC) on lysine mono- and dihydrochloride solutions was measured and the amount of positively charged lysine which had penetrated into a DMPC monolayer was calculated by successive approximation. The amount of penetration was smaller for lysine monohydrochloride than for the dihydrochloride. Moreover, both were smaller than that of uncharged lysine because mono- and dihydrochloride are more hydrophilic than uncharged lysine. The average area per molecule in the monolayer consisting of lysine and DMPC, A23, was obtained. In the case of charged lysine, A23 increased with the mole fraction of lysine in a monolayer, X2, in contrast it decreased with X2 in the case of uncharged lysine. The partial molecular area of positively charged lysine was considerably larger than that of uncharged lysine. This indicates that the remarkable expansion of a monolayer is caused by the penetration of positively charged lysine because of electrostatic repulsion in the monolayer. The effect of sodium chloride on the adsorption of lysine was also investigated, but the amount adsorbed was independent of the presence of 0.5 mol dm−3 sodium chloride.
  • Kazuyori Konishi, Kensuke Takahashi
    1983 年 56 巻 6 号 p. 1612-1615
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    The 13C and 1H NMR spectra have been observed for the title anions with lithium as a counter ion in polar solvents. Two kinds of anions are formed by lithium-proton exchange and addition of butyllithium. The charge distributions in the anions are discussed in terms of the σ-included ω-HMO method. The former anions can be regarded as picolyl-type carbanions, but the latter ones are ionic species having two of three basic characteristics on picolyl-type carbanions.
  • Hiroshi Sakai, Yutaka Maeda, Taka-aki Kobayashi, Hideki Shirakawa
    1983 年 56 巻 6 号 p. 1616-1619
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    Mössbauer spectra of FeCl3-doped polyacetylenes [CH(FeCl3)y]x (y=0.074, 0.087, and 0.13), which exhibit high electrical conductivities of ≈800, ≈800, and ≈100 S/cm at room temperature, have been measured at the temperatures of 290, 196, 78, and 5 K, respectively. The spectra consist of a superposition of two quadrupole-split doublets, described as doublet (A) and doublet (B), at 290, 196, and 78 K. At 5 K the doublet (A) splits into six lines arising from the magnetic hyperfine interaction, whereas the doublet (B) still remains paramagnetic. The doublet (B) increases remarkably in the Mössbauer absorption with decreasing temperature and is predominant. The values of the isomer shift, the quadrupole splitting, and the internal magnetic field, indicate that the iron compounds corresponding to the doublet (A) and (B) are FeCl2·nH2O (n=1 and/or 2) and FeCl4, respectively. These results established that the mechanism of the FeCl3-doping process in polyacetylene is as follows:
    2FeCl3+e→FeCl4+FeCl2,
    FeCl2+nH2O→FeCl2·nH2O(n=1 and/or 2).
  • Koichiro Miyajima, Masahiro Sawada, Masayuki Nakagaki
    1983 年 56 巻 6 号 p. 1620-1623
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    Activity coefficients of isomeric monosaccharides, D-glucose, D-mannose, and D-galactose were determined by isopiestic comparison method at 25 °C. Excess partial molar entropy of water (\barSwex) of each monosaccharide solution was negative and the absolute value increased with concentration of solute. From the magnitudes of negative \barSwex, it was concluded that the structure making ability among three isomers lies in the order D-glucose>D-mannose>D-galactose.
  • Hemlata Mohabey, Pramod Kumar Sharma, Rajendra Kumar Mishra
    1983 年 56 巻 6 号 p. 1624-1626
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    A simple, rapid, and accurate method has been developed for the gravimetric determination of Copper(II) using a new reagent N1-hydroxy-N1-(m-tolyl)-N2-(o-chlorophenyl)-p-toluamidine hydrochloride (HTCPTH). The proposed reagent reacts quantitatively with copper at 3.3–11.0 pH giving a buff coloured precipitate. The precipitated complex can be easily filtered, dried and directly weighed as (C21H18N2OCl)2Cu. The complex is thermally stable as is evident from DTA and TGA studies up to 210 °C and insoluble in many organic solvents. Most of the common ions including Ni(II), Co(II), Cr(III), Mn(II), etc. do not interfere. The interference due to iron(III) can be eliminated by masking it with tartaric acid. The method has been successfully applied for the determination of copper in some British Chemical Standards alloys.
  • Mikiya I, Hisanobu Wakita, Isao Masuda
    1983 年 56 巻 6 号 p. 1627-1631
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    The thermal behavior in the solid state of the title complexes was investigated. Here 2,3-alkanedione dioximato is CH3–C(=NOH)–C(=NO)–R; R includes C2H5 (1), n-C3H7 (2), n-C4H9 (3), n-C5H11 (4), n-C6H13 (5), and n-C8H17 (6) groups. The complexes, 1, 2, 5, and 6, underwent thermal crystal structure transformation; the transformation was irreversible for 1 and 5, and reversible for 2 and 6. The ΔHt values, heats of transformation, were found to fall in the 5.3–32.6 kJ mol−1 range. The ΔHm values, heats of melting, were determined for the complexes, 26. On the basis of these data, the thermal characteristics for these complex crystals are discussed in relation to the nature of the R groups.
  • Etsuro Kobayashi, Shinsuke Yamazaki
    1983 年 56 巻 6 号 p. 1632-1636
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    The formation region, dehydration behavior, and lattice constants of various types of titanium(IV) bis(hydrogenorthophosphate) hydrates were investigated. α-Ti(HPO4)2·H2O was formed by refluxing an amorphous titanium phosphate (ATP) with H3PO4 at 110–165 °C or by treating it with H3PO4 (up to 11.5 mol dm−3) under hydrothermal conditions at temperatures up to 250 °C. (β-γ)-Ti(HPO4)2·xH2O was obtained by refluxing ATP with H3PO4 (15–16 mol dm−3) above 165 °C. γ-Ti(HPO4)2·2H2O was formed by a hydrothermal reaction of ATP and H3PO4 (10–16 mol dm−3) at 200–300 °C. In the thermal analysis of Ti(HPO4)2, no difference in weight loss was found at temperatures up to 920 °C of α-form irrespective of the drying conditions of the samples. The (β-γ)-form dried under reduced pressure over P2O5 had a composition corresponding to that of a 1/2 hydrate. The γ-form dried at a relative humidity of 75% had a composition identical to that of the dihydrate. In view of the X-ray diffraction, it seemed that the (β-γ)-form (11.6 and 9.2 Å) was changed by drying under reduced pressure over P2O5 to the β-form (9.2 Å) as anhydride. The γ-form (11.6 Å) was dehydrated to the β-form by heating. The change in the inter-layer distance upon dehydration was also confirmed by means of a that of the electron diffraction. Thus, it was considered that the (β-γ)-form was a mixture as a quasi stable form.
  • Hisayoshi Nakai
    1983 年 56 巻 6 号 p. 1637-1641
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    The crystal structure of the title compound was determined by means of the X-ray diffraction technique. The crystal is triclinic, space group P\barl, a=11.288(8), b=15.186(17), c=7.368(4) Å, α=74.93(3), β=78.23(3), γ=65.92(3)°, and Z=2. The structure was solved by the heavy-atom method and refined by the least-squares method to R=0.068 for 3678 non-zero reflections. The crystal is composed of BF4 ions and polymeric chains of [Cu(BF4)(bpy)2+] in which a tetrafluoroborate ion bridges two adjacent copper atoms through its two fluorine atoms. The coordination polyhedron around the copper atom is a tetragonally distorted octahedron; the four nitrogen atoms of bipyridine molecules in the equatorial plane are arranged in a flattened tetrahedral manner (average Cu–N=1.99 Å) and the two axial Cu–F distances are 2.566(6) and 2.662(4) Å. In both bipyridine molecules, the two pyridine rings are twisted slightly from each other; the interplanar angle is 3.1° in one bipyridine ligand and 10.2° in the other.
  • Michio Nakamura, Hisashi Okawa, Sigeo Kida
    1983 年 56 巻 6 号 p. 1642-1645
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    Metal complexes, M(l-moba)2(H2O)n (M=Cu(II), n=0; Ni(II), n=2; Pd(II), n=0) and M(bpy)(l-moba)ClO4 (M=Cu(II), Pd(II)), where H(l-moba) denotes 1-l-menthyloxy-3-benzoylacetone, have been synthesized and characterized by means of elemental analyses, NMR spectra, electronic spectra, and circular dichroism spectra. In the NMR spectra of H(l-moba), Pd(l-moba)2, and Pd(bpy)(l-moba)ClO4, the methylene protons adjacent to the l-menthyloxy group were observed as AB quartet. The chloroform solutions of Cu(l-moba)2 and Cu(bpy)(l-moba)ClO4 showed a positive CD band at 15500 and 16200 cm−1, respectively. The chloroform solution of Ni(l-moba)2(H2O)2 also showed a weak, positive CD band near 16000 cm−1. When pyridine or t-butylamine was added to the chloroform solution of Cu(l-moba)2, a negative CD appeared around 17000 cm−1 attributable to the five-coordinate species Cu(l-moba)2B. On the other hand, with adding an amine to the chloroform solution of Ni(l-moba)2(H2O)2, the 16000 cm−1 CD band decreased its intensity and finally disappeared. Similar trend was observed when alcohol, DMSO, or DMF was added to the chloroform solution of Ni(l-moba)2(H2O)2. NMR and CD spectral results have been rationalized by assuming that the l-menthyl group interacts with the chelate ring of l-moba and this interaction gives rise to a chirality around the metal ion.
  • Shinji Izumoto, Ushio Sakaguchi, Hayami Yoneda
    1983 年 56 巻 6 号 p. 1646-1651
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    The reversed-phase ion-pair chromatography with cinchona alkaloid cations as the ion-pairing reagents has been used to resolve optically several anionic complexes of the type cis(N)-[Co(N)2(O)4]. Complete optical resolution has been achieved for [Co(edta)], cis-[Co(ida)2], [Co(cydta)], [Co(ox)2(en)], and cis-α-[Co(ox)(edda)] by quinine, quinidine, and cinchonidine but not by cinchonine, where edta=ethylenediaminetetraacetate, ida=iminodiacetate, cydta=trans-1,2-cyclohexanediaminetetraacetate, ox=oxalate, en=ethylenediamine, and edda=N,N′-ethylenediaminediacetate. The adjusted retention volumes have been measured for the enantiomers. From comparison of the retention volumes and separation factors obtained for the alkaloids and their derivatives, the mode of chiral discrimination has been proposed.
  • Masaharu Ueno, Tomomi Yasui, Isamu Horikoshi
    1983 年 56 巻 6 号 p. 1652-1656
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    Kinetics of valinomycin- and tetranactin-mediated cation transport were studied. An equation was derived which describes the kinetics of ionophore induced cation leakage from liposomes. The theoretically predicted ion-selectivity of the ionophore-mediated cation transport agreed well with that given by experiments. This supports the assumptions used in the derivation and is consistent with the following characteristics of the ionophores: (1) Ionophore-mediated cation transport is carried out by stoichiometrically forming a ternary complex between ionophore, cation and lipophilic anion. (2) The ion-selectivity of the ionophore is determined primarily by the formation constant of the ionophore cation complex in water. (3) A relative value of the complex formation constant in water can be calculated from both the complex formation constant in methanol, which is estimated more easily than that in water, and the difference between desolvation energy of the cation in water and methanol.
  • Kazuki Sato, Ukon Nagai, Tsutomu Higashijima
    1983 年 56 巻 6 号 p. 1657-1660
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    To confirm the general applicability of CD spectra of N-(2,4-dinitrophenyl(Dnp))tetrapeptide p-nitroanilides (pNA’s) to the analysis of β-turn preference of the tetrapeptide sequences, Dnp-pNA derivatives of some tetrapeptides related to β-turn preferring sequences in proteins were synthesized and subjected to CD and 1H NMR measurements. CD spectra of Dnp–Gly–L-Pro–L-Asn–Gly–pNA (5a) were just the mirror image of those of gramicidin S-model peptide, Dnp–Gly–D-Ala–L-Pro–Gly–pNA (6). This suggested that 5a strongly preferred the β-turn and the type of turn was different from that of 6. The relative intensities of Cotton effects of the tetrapeptide with the general structure Dnp–Gly–L-Pro–Y–Gly–pNA (Y=L-Asn, Gly, L-Ala, or L-Gln) roughly agreed with the bend potentials of the amino acid residues at the third position of β-turns in proteins reported by Chou and Fasman. The effects of changing the amino acid residues at the second position of β-turn were also examined.
  • War\={o} Nakanishi, Yoshitsugu Ikeda
    1983 年 56 巻 6 号 p. 1661-1664
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    Long-range coupling constants between 77Se and 13C in selenoanisole, diphenyl selenide, diphenyl diselenide, and their 2-mono- and 2,2′-disubstituted derivatives, selenoxanthone, selenanthrene, dichlorides, and selenoxides were measured to disclose predominant factors governing the magnitude of the coupling. Extraordinary large values for two- and three-bond couplings are found in selenoxanthone. Three factors are operative: the orientational effect, the coordination number, and the effect of ring formation. The last factor accompanies a stronger inverse effect on the coupling of selenoxides than on that of selenides.
  • Mitsuo Sado, Hideaki Abe, Nobuki Inuzuka, Kozo Shirai, Takanobu Kumamo ...
    1983 年 56 巻 6 号 p. 1665-1668
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    It was found that the Claisen rearrangement of the lithium enolate of 1-(2-thienyl)alkyl alkanoate in refluxing THF resulted in the formation of 2-(3-thienyl)alkanoic acid (2). Similarly, when the lithium enolate of 4-(2-thienyl)-4-butanolide was stirred at room temperature in the presence of hexamethylphosphoric triamide, 5,6-dihydro-4H-cyclopenta[b]thiophene-4-carboxylic acid was obtained. Further, it was found that the Birch reduction of 2 and subsequent alkylation with benzyl bromide gave a regioselective ring-opening product, 4-benzylthio-3-ethyl-3-alkenoic acid, in a good yield. The Birch reduction of 2-thienylacetic acid, followed by alkylation with benzyl bromide, also gave (Z)-3-benzylthio-3-hexenoic acid as the main product.
  • Toyonori Takebayashi, Nobuharu Iwasawa, Teruaki Mukaiyama, Tadashi Hat ...
    1983 年 56 巻 6 号 p. 1669-1677
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    The intramolecular Diels-Alder reactions between acyclic dienes and α,β-unsaturated amides utilizing the internal coordination of the metal salts have been studied in detail. When the magnesium salts of N-(trans, trans-2,4-alkadienyl)-N-(2-hydroxyphenyl)acrylamide derivatives are employed, the intramolecular Diels-Alder reactions are remarkably accelerated and the corresponding cycloadducts are obtained in high yields with isomeric ratios (exo-adducts: endo-adducts) of about 3 : 2. And the same reactions of N(trans, trans-2,4-alkadienyl)-N-(2-hydroxyphenyl)-1-cyclopentenecarboxamide afford predominantly (60 : 40 to 85 : 15 selectivity) trans-fused cycloadducts (exo-adducts) in good yields.
  • Ichizo Miyake, Katsushige Kouge, Hidenori Kanehisa, Hideo Okai
    1983 年 56 巻 6 号 p. 1678-1681
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    In order to elucidate the relationship between chemical structure and bitter taste of BPIa, the analogs containing D-proline or glycine in place of the L-proline in the 3- or 4-positions were synthesized. The bitter taste of [D-Pro3,4]–BPIa (lD-D), [D-Pro3]–des–Pro3–BPIa (2D), and [Gly3]–des–Pro3–BPIa lacking the L-proline residue was much weaker than that of the peptides containing the L-proline, BPIa (1L-L), 1L-D, 1D-L, and 2L. The CD curves of these analogs and BPIa were measured in water. The results suggested that the bitter taste of BPIa is caused by the spatial structure attributed to the L-proline residue.
  • Hiroshi Nishino, Kazu Kurosawa
    1983 年 56 巻 6 号 p. 1682-1687
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    The reaction of 2-(methylamino)benzophenone with manganese(III) acetate afforded 5-[(o-benzoylanilino)methyl]-2-(methylamino)benzophenone, 2-aminobenzophenone, 5-formyl-2-(methylamino)benzophenone, 2-amino-5-[(o-benzoylanilino)methyl]benzophenone, 2-formamidobenzophenone, 2-amino-5-formylbenzophenone, and 2-(N-methylformamido)benzophenone. It was found that the reaction did not cause oxidative cyclization, but dimerization and conversion of N-methyl into N-formyl groups. Characterization of the products, the detailed oxidation mechanism, and the effects of the additives are discussed.
  • Otohiko Tsuge, Minoru Tanaka, Hiroshi Shimoharada, Shuji Kanemasa
    1983 年 56 巻 6 号 p. 1688-1693
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    Reactions of 2-methylene-3-phenacylbenzothiazoline and 3-benzyl-2-methylenebenzothiazoline, generated in situ from the corresponding 2-methylbenzothiazolium bromide and triethylamine, with methylenecyclopropenes gave a variety of products, cross-conjugated systems, spiro-cyclopentafurans and/or cyclopentabenzothiazines, depending on the nature of substituents of the methylenecyclopropenes. The reaction pathways for the formation of products are also described.
  • Seiji Shinkai, Yuichi Ishikawa, Osamu Manabe
    1983 年 56 巻 6 号 p. 1694-1699
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    A new metal-coordinative flavin(2,4,7-trimethylquino[8,7-g]pteridine-9,11(7H,10H)-dione: (1)) which has a phenanthroline-like skeleton within the molecular structure was synthesized. Being different from conventinal flavins, the new flavin showed a significant affinity toward metal ions and the absorption spectra were sensitively affected by added metal ions. The spectral patterns were classified into three types, which were assigned respectively to the different coordination structures. It was demonstrated through oxidation of dihydropyridine derivatives, phenylhydrazine, and L-ascorbic acid that complexed metal ions are able to “activate” 1 as oxidizing agent. The complexes with Zr4+ and Fe3+ even oxidized alcohols at ambient temperature. Unexpectedly, it was found that tetrahedral coordination metals such as Cd2+, Zn2+, and Co2+ frequently give the stable semiquinone radical of 1. The remarkable stabilization effect of these metals was attributed to a bent, butterflywing structure of the semiquinone radical. These findings suggest that the 1–metal complexes are useful not only as a model system of metalloflavoproteins but also as an in vitro oxidation catalyst.
  • Seiji Shinkai, Yoshihiro Honda, Takahide Minami, Kaori Ueda, Osamu Man ...
    1983 年 56 巻 6 号 p. 1700-1704
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    Cylindrical and phane crown ethers with azobenzene segments as a light-switch functional group were synthesized. Cylindrical ionophores in which two diazacrown ethers are linked by two photoresponsive azobenzene pillars change their binding ability for polymethylenediammonium salts in response to photoirradiation. Thus, the distance between the two crown rings can be photocontrolled. A phane-type ionophore in which 1,23-bis(p-aminophenoxy)-3,6,9,12,15,18,21-heptaoxatricosane is linked by a trans-4,4′-azobenzenedicarbonyl segment exhibits no affinity with all alkali metal cations but significantly binds Rb+ and Cs+ under UV-light irradiation. This is the example of the “all-or-nothing” control of the ion-binding ability and implies that a crown-like loop emerges only when the azobenzene segment is photoisomerized to the cis-configuration. These ionophores are categorized to novel photoresponsive crown ethers.
  • Kuniaki Itoh
    1983 年 56 巻 6 号 p. 1705-1709
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    The photo-induced addition reaction of 1,4-dibromo-2,5-piperazinedione (1) with cyclohexene in acetonitrile gave 1 : 1-adducts[1-(2-bromocyclohexyl)-2,5-piperazinediones] and 1 : 2-adducts[1,4-bis(2-bromocyclohexyl)-2,5-piperazinediones] besides 3-bromocyclohexene, 1,2-dibromocyclohexane, and a solvent-incorporated product, trans-2-acetylamino-2-bromocyclohexane. Stereochemistry of the adducts was elucidated and mechanism of the addition reaction was discussed.
  • Seiichiro Ogawa, Tatsushi Toyokuni, Masayasu Ara, Masaru Suetsugu, Tet ...
    1983 年 56 巻 6 号 p. 1710-1714
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    The title substituted 1,3-cyclohexadiene was prepared in three steps from the readily available DL-1,2-di-O-acetyl-(1,3/2)-3-bromomethyl-5-cyclohexene-1,2-diol. Epoxidation of it with m-chloroperoxybenzoic acid in 1,2-dichloroethane afforded several stereoisomers of the biologically interesting highly oxygenated cyclohexane derivatives.
  • Hiroshi Awano, Katsumichi Ono, Kenkichi Murakami
    1983 年 56 巻 6 号 p. 1715-1720
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    Conductivities of NaSCN and KSCN solutions have been measured in ethanol and nitromethane in the presence of poly(oxyethylene). For poly(oxyethylene)–KSCN solutions in ethanol and nitromethane, a distinct minimum appears in conductivity vs. polymer concentration curves. In addition, for a poly(oxyethylene)–NaSCN solution in nitromethane, the conductivity curve rises steeply after passing through the minimum. These anomalies cannot be explained by the cation binding to the polymer alone, and the ionic association on the polymer chain should be taken into account at the same time. In order to analyze the results, a theory based on the duplicate ion binding on a one-dimensional lattice has been developed. The theory not only predicts the appearance of the conductivity minima, but also makes it possible to estimate the ionic association constants.
  • Tsunenori Nozawa, Masahiro Hatano, Unpei Nagashima, Shigeru Obara, Hir ...
    1983 年 56 巻 6 号 p. 1721-1727
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    Ab initio LCAO-SCF-MO calculations of a model oxyheme were carried out on several singlet, triplet and quintet states arising from the three types of configurations, (dε)6ga)2, (dε)5(dγ)1ga)1gb)1, and (dε)5ga)2gb)1. The lowest states in the SCF energy are of the configuration (dε)5ga)2gb)1 whose electronic structures can be also expressed as Fe(III)–O2 from the results of Mulliken’s population analysis. Calculated Mössbauer parameters of those states are in good agreement with experiments for oxyhemoglobin, oxymyoglobin and model oxyheme, while those of the closed-shell singlet state (dε)6ga)2 are inconsistent with experiments. The Fe–O1 overlap populations indicate a bonding nature for the former states and a non-bonding nature for the latter state. These results all predict singlet states of Fe(III)–O2 structure as the main configuration of the ground state in the model oxyheme.
  • Hiromitsu Terao, Masanori Fukura, Tsutomu Okuda, Hisao Negita
    1983 年 56 巻 6 号 p. 1728-1731
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    The Zeeman effect on 81Br NQR in a single crystal of PBr3·BBr3 was studied at room temperature. The crystal has an orthorhombic symmetry. The bond angles have been found to be 111.2±0.1° and 111.5±0.1° for Br–B–Br, and 107.0±0.1° and 109.1±0.3° for Br–P–Br. The Br atoms of BBr3 group have relatively large values of η, 0.151±0.004 and 0.120±0.007, while the Br atoms of PBr3 group have small values, 0.025±0.005 and 0.020±0.004. The large η values of Br atoms of BBr3 group are ascribed to the π bonding existing in the B–Br bonds.
  • Kazuaki Harata, Kaneto Uekama, Masaki Otagiri, Fumitoshi Hirayama
    1983 年 56 巻 6 号 p. 1732-1736
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    The crystal structure of heptakis(2,3,6-tri-O-methyl)-β-cyclodextrin–p-iodophenol (1 : 1) tetrahydrate, C63H112O35·C6H5OI·4H2O, was determined by the X-ray method. The crystal is orthorhombic with the space group P212121, Z=4, a=14.997(2), b=21.368(2), and c=28.205(3) Å. The structure was solved by the heavy atom method combined with the rigid-body least-squares technique and refined by the block-diagonal least-squares method to the final R-value of 0.094 for 3268 reflections (sinθ⁄λ<0.49). Heptakis(2,3,6-tri-O-methyl)-β-cyclodextrin is in the shape of a truncated elliptical cone. The macrocyclic ring is remarkably distorted from a regular heptagonal structure. The iodophenyl group of the guest is inserted into the host cavity. The phenolic hydroxyl group protrudes from the cavity, forming hydrogen bonds with two water molecules. The iodine atom is located at the center of the macrocyclic ring, while the benzene ring occupies its position at the base side of the cone. The crystal is built up of columns which are formed by the stack of host molecules in a head-to-tail mode along the two-fold screw axis which is parallel to the crystallographic b axis. Four water molecules fill intermolecular spaces in the crystal.
  • Masako Tanaka, Susumu Sasaki, Meiseki Katayama
    1983 年 56 巻 6 号 p. 1737-1739
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    The near infrared emission spectra of Xe and Xe–Ar which were excited by the pulsed irradiation of electrons by using a 45 MeV linear accelerator were investigated. A new broad band, probably due to the transition between the upper molecular states, was observed at 1200 to 1400 nm. The effects of O2 and SF6 on this band were studied.
  • Kunio Fukushima, Hisayo Sasaki
    1983 年 56 巻 6 号 p. 1740-1744
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    Raman spectra of N-methylpyrrolidine were measured in various states and a normal vibration calculation was carried out on its conformers. Results of the measurement and calculation indicate that the Raman band of the inversion vibrational mode is caused to shift remarkably by the formation of hydrogen bond to the nitrogen atom. This phenomenon, along with the enthalpy of hydrogen bond formation obtained from measurements at various temperatures, suggests that the conformer predominant in pure liquid corresponds to one minimum in the potential for the inversion motion, which has a low potential barrier and high anharmonicity.
  • Yoshio Sasada, Akio Takenaka, Toshio Furuya
    1983 年 56 巻 6 号 p. 1745-1748
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    The copper(II) complex containing L-histidine and L-serine crystallizes from an aqueous solution. Crystals of aqua(L-histidinato)(L-serinato)copper(II) trihydrate are monoclinic, space group P21, a=11.046(2), b=7.315(1), c=9.737(1) Å, β=101.34(2)° and Z=2. A square-planar coordination around copper consists of α-amino nitrogen and δ-nitrogen atoms in histidine and α-amino nitrogen and α-carboxyl oxygen atoms in serine, the two amino groups being in cis position. The fifth coordination site is occupied by a water molecule, and the carboxyl oxygen atom of serine in the adjacent complex makes a weak bond with copper to complete a distorted octahedron. The chelating scheme and overall crystal structure are the same as those of (L-alaninato)aqua(L-histidinato)copper(II) trihydrate (1). Crystallization water molecules are situated on the fixed positions in the void space surrounded by the columns of the complexes, but the hydroxyl group of serine takes two sites randomly. The common chelating scheme in the present crystal and 1 is in correspondence with the observation that serine and alanine are of moderate cooperativity with histidine in forming the ternary complexes.
  • Toshiki Wakabayashi, Katsuko Takaizumi
    1983 年 56 巻 6 号 p. 1749-1752
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    The osmotic and activity coefficients have been obtained cryoscopically for (n-Bu)4−nPhnPX(n=0–4, X=Cl, Br) in aqueous solutions at freezing point. The γ± decreases with increasing n, for both the chloride and the bromide salts. With the chloride salts, γ±’s for the salts of n from 0 to 2 show positive deviation from the Debye-Hückel limiting law as concentration increases, whereas γ±’s for others show negative deviation. Replacement of the anion from Cl to Br results in lower γ±’s for the salts of n from 0 to 2, but this elevates the other γ±’s. These results were interpreted qualit tively in terms of the cosphere overlap model by Desnoyers et al., by assuming a hydrophilic character of the present phenyl group. An attempt was made to evaluate the pairwise interaction coefficients(B*) and to estimate the contributions to B* from the interactions, butyl-Cl and phenyl-Cl.
  • Takashi Kakiuchi, Mitsugi Senda
    1983 年 56 巻 6 号 p. 1753-1760
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    Electrocapillary curves at the polarized interface between a nitrobenzene solution of tetrabutylammonium tetraphenylborate (TBATPB) and an aqueous solution of lithium chloride at various concentrations of TBATPB and LiCl have been measured by the drop time method using a dropping electrolyte solution electrode at 25 °C. The relative surface excesses of tetrabutylammonium and tetraphenylborate ions in the nitrobenzene phase and of lithium and chloride ions in the aqueous phase were well described by the Gouy-Chapman theory of diffuse layers for both sides of the interface. A model of the electrical double layer for the nitrobenzene–water interface is presented, in which an ion-free inner layer consisting of laminated monolayers of water and nitrobenzene is sandwiched by the two diffuse layers on each side of the interface. The potential difference across the inner layer, which was estimated to be ca. 20 mV at the potential of zero charge, was found to be dependent on the surface charge density and to be nearly independent of the electrolyte concentration.
  • Tadaaki Kakutani, Isao Katasho, Mitsugi Senda
    1983 年 56 巻 6 号 p. 1761-1767
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    The electrochemical redox reaction of flavin–adenine dinucleotide (FAD) adsorbed on a hanging mercury drop electrode was studied in a pH 6.9 phosphate buffer by means of cyclic d.c. and a.c. voltammetry. Both the oxidized and reduced forms of FAD were strongly adsorbed on the mercury electrode surface. At the surface concentrations of FAD, Γ, lower than 5.0×10−11 mol cm−2, the cyclic d.c. and a.c. voltammetric behavior of adsorbed FAD was explained by the theory for a two-step one-electron surface redox reaction. The formal redox potential, semiquinone formation constant, and charge transfer rate constant for the surface redox reaction of FAD and the interaction parameter of adsorbed FAD species were determined. Cyclic d.c. voltammetry and differential capacity measurement showed that, as Γ exceeded 5×10−11 mol cm−2, the reorientation of adsorbed FAD molecules occurred. At Γ>5.8×10−11 mol cm−2, the semiquinone formation constant was very small and the behavior was interpreted by the theory of a single-step two-electron surface redox reaction. The electrochemical surface redox properties of FAD adsorbed on a mercury electrode surface appear to depend on the orientation mode of adsorbed FAD molecules.
  • Shinji Tomoda, Katsumi Kimura
    1983 年 56 巻 6 号 p. 1768-1771
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    A photoelectron spectroscopic method is proposed to estimate the ratio of number densities between the monomer and the dimer produced in the supersonic jet. Approximate monomer-dimer ratios have been estimated for water, methanol and formic acid by assuming that the photoionization cross sections of the monomer and dimer are equal to each other. The results show reasonable agreement under similar conditions to those available from mass spectrometric analyses of fragmentation patterns. A simple temperature-controlled supersonic nozzle beam source is described here, which enables us to produce hydrogen-bonded dimers in measurable amounts.
  • Yoshihisa Yamamoto
    1983 年 56 巻 6 号 p. 1772-1774
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    The reactions of (C6H5)3P=CH2 (L) with BeCl2 or MgCl2 in the mole ratio of 2 : 1 or 4 : 1 yield new dimeric compounds of di-μ-chloro-bis[(methylenetriphenylphosphorane)metal] dichloride, (Remark: Graphics omitted.) (M: Be and Mg). The configuration of these metals is trigonal. The reactions of L with AlCl3, GaCl3 or InCl3 in the mole ratio of 2 : 1 yield new compounds of di-μ-chloro-bis[bis(methylenetriphenylphosphorane)metal] tetrachloride, (Remark: Graphics omitted.) (M: Al, Ga, and In). The reactions of L with AlCl3 or GaCl3 in the mole ratio of 3 : 1 or 5 : 1 yield new compounds of μ-chloro-bis[tris(methylenetriphenylphosphorane)metal] pentachloride, [{(C6H5)3PCH2}3M–Cl–M{CH2P(C6H5)3}3]Cl5 (M: Al, Ga). These dimers, bridged by chloride anions, are thermally stable.
  • Yasukazu Yokoyama
    1983 年 56 巻 6 号 p. 1775-1779
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    Some derivatives of pyrido[1′,2′: 1,2]pyrimido[4,5-b]acridine-7,15-diones have been synthesized, their absorption spectra have also been investigated in order to elucidate the relationship between the color and the chemical constitution in contrast to the related compounds, quinacridone and pyrido[2,1-b]pyrido[1′,2′ : 1,2]pyrimido[4,5-g]quinazoline-7,15-dione. The absorption spectra in DMSO and in concentrated sulfuric acid show a good correlation with the electronic effect of the substituents. The absorption spectra of the solid are more influenced by the position of the substituents than by the electronic effect.
  • Teruyuki Hayashi, Masato Tanaka, Ikuei Ogata, Teruyuki Kodama, Tamotsu ...
    1983 年 56 巻 6 号 p. 1780-1785
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    An X-ray molecular structure analysis of [(2R, 3R)-2,3-O-isopropylidene-1,4-bis(5H-dibenzophosphol-5-yl)-2,3-butanediol((−)-DIPHOL)](1,5-cyclooctadiene)chloroiridium(I) was carried out. The complex takes a distorted trigonal bipyramidal structure, and the chelate ring of (−)-DIPHOL makes a chair form, which decreases the distances of atoms in the chelate ring from the P–Ir–P coordination plane. Thus, the chiral coordination structure of DIPHOL becomes remarkably different from that of DIOP. Through a comparison of the results of X-ray analyses, the results obtained in asymmetric hydroformylation (predominant absolute configuration and optical yield of products) catalyzed by the rhodium-complexes were explained on the basis of some well-grounded assumptions.
  • Kohji Yoshinaga, Taketoshi Kito, Katsutoshi Ohkubo
    1983 年 56 巻 6 号 p. 1786-1790
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    Asymmetric transfer hydrogenations of α,β-unsaturated acids (MeCH=C(Me)CO2H, PhCH=C(Me)CO2H, CH2=C(CH2CO2H)CO2H, and HO2CCH=C(Me)CO2H) and esters (MeCH=C(Me)CO2R; R=achiral and chiral group) by alcohols (PhCH2OH, (RS)-PhCH(Me)OH, and α-D-glucofuranose derivatives) were carried out with RuCl2(PPh3)3 or Ru2Cl4((+) or (−)-diop)3 (diop=2,3-O-isopropylidene-1,4-bis(diphenylphosphino)-2,3-butanediol) at 160–190 °C. The optical purity (3.4–16.4%) of hydrogenated acids obtained with PhCH2OH and Ru2Cl4((−)-diop)3 is in the order MeCH=C(Me)CO2H>PhCH=C(Me)CO2H>CH2=C(CH2CO2H)CO2H>HO2CCH=C(Me)CO2H, suggesting that the substrates possessing two carboxyl groups would provide an asymmetrically unfavorable coordination to the Ru(II) complex for this asymmetric reaction. In the transfer hydrogenation of MeCH=C(Me)CO2R by PhCH2OH or (RS)-PhCH(Me)OH at 190 °C, the extent of asymmetric induction of Ru2Cl4((−)-diop)3 (1.7–11.4% e.e. with PhCH2OH and 7.4–18.2% e.e. with (RS)-PhCH(Me)OH) decreases with increase in bulkiness of groups R (R=H, Me, Et, n-Bu, and PhCH2) and is not enhanced by the introduction of any groups R with chiral carbon atoms into esters (maximum 15.4% e.e.). The structural change of hydrogen donors from PhCH2OH to (RS)-PhCH(Me)OH appreciably increases the optical purity of the saturated acids and esters, and the chiral α-D-glucofuranose derivatives afford optically active saturated products, even with achiral RuCl2(PPh3)3. Features of the present reaction are discussed in relation to the reaction mechanism.
  • Shohei Satoh, Hiroshi Suginome, Masao Tokuda
    1983 年 56 巻 6 号 p. 1791-1794
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    Electrolysis of allyl chloride and five molar excess of acetone in hexamethylphosphoric triamide containing 0.5 M tetrabutylammonium perchlorate gave an addition product, 2-methyl-4-penten-2-ol, in a 53% yield. Allyl groups of 1-chloro-2-methyl-2-propene, 1-chloro-2-butene(3), 3-chloro-1-butene(4), 1-chloro-3-methyl-2-butene(5), and 3-chloro-3-methyl-1-butene(6), and benzyl groups of benzyl chloride, benzyl bromide, and 1-chloro-1-phenylethane can similarly be added to acetone by electrolysis to give the corresponding alcohols in fair to good yields. Among these electrochemical reactions, those of 3, 4, 5, and 6 with acetone give respectively two isomeric homoallyl alcohols, one of the isomers is not accessible by the usual chemical reaction between allylic organometallics and acetone.
  • Takeo Akiyama, Yasuki Yoshida, Tokiko Hanawa, Akira Sugimori
    1983 年 56 巻 6 号 p. 1795-1798
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    The treatment of 1,1,1,3-tetrachloro-3-phenylpropane with alkali in ethanol affords ethynyl phenyl ketone and its acetal in good yields. This reaction proceeds through the elimination of hydrogen chloride and an efficient 1,3-proton transfer catalyzed by base. Ethyl cinnamate is obtained in only 2% yield.
  • Hiroshi Seto, Taisuke Okuda, Tomoyuki Takesue, Tadashi Ikemura
    1983 年 56 巻 6 号 p. 1799-1802
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    The reactions of malonaldehyde with guanosine and 2′-deoxyguanosine proceed slowly under acidic conditions to give new pyrimidopurine nucleosides, 3a and 3b, respectively. These compounds emit strong yellow fluorescence and are hydrolyzed by NaOH into malonaldehyde and guanosine from 3a (2′-deoxyguanosine from 3b). From chemical and spectroscopic evidence, these compounds were deduced to be 3-β-D-ribofuranosylpyrimido[1,2-a]purin-10(3H)-one (3a) and 3-(2-deoxy-β-D-erythro-pentofuranosyl)pyrimido[1,2-a]purin-10(3H)-one (3b). No products were detected in the reaction mixture of malonaldehyde with 1-methylguanosine, adenosine, cytidine, uridine, thymidine, 2′-deoxyadenosine, or 2′-deoxycytidine.
  • Sumio Yokota, Mitsuru Nishida, Oyo Mitsunobu
    1983 年 56 巻 6 号 p. 1803-1806
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    Reaction of methyl 2,3-anhydro-4,6-dideoxy-α-D-ribo-hexopyranoside with MgI2 exclusively afforded methyl 3,4,6-trideoxy-3-iodo-α-D-xylo-hexopyranoside which was dehalogenated by treatment with LiAlH4 to give methyl 3,4,6-trideoxy-α-D-erythro-hexopyranoside (2). Hydrolysis of 2 and subsequent treatment with ethoxycarbonylmethylenetriphenylphosphorane gave ethyl (2E, 4R, 7R)-4,7-dihydroxy-2-octenoate (10). Oxidation of 10 by-active MnO2 resulted in the formation of an equilibrium mixture of ethyl (2E, 7R)-7-hydroxy-4-oxo-2-octenoate (the carbon skeleton of pyrenophorin) and cyclic hemiacetal. On treatment with acetic anhydride, the mixture afforde dethyl (2E, 7R)-7-acetoxy-4-oxo-2-octenoate.
  • Yoshiaki Takahashi, Tsutomu Tsuchiya, Yukiko Suzuki, Sumio Umezawa, Ha ...
    1983 年 56 巻 6 号 p. 1807-1811
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    The titled compounds were prepared from 3,6′-bis(N-benzyloxycarbonyl)-3″-N-(trifluoroacetyl)kanamycin A (1). Oxidation of 1 with hydrogen peroxide in the presence of sodium tungstate gave the 1-hydroxyimino derivative, which, after deblocking, gave 1-deamino-1-dehydro-1-hydroxyiminokanamycin A (6). Reduction of 6 with Raney nickel–hydrogen in aqueous ammonia gave a mixture of kanamycin A and 1-epikanamycin A (9), which were separated through derivation to the corresponding tetrakis-N-(t-butoxycarbonyl) derivatives, which showed different solubility in chloroform. 1-N-[(S)-4-Amino-2-hydroxybutyryl]-1-epikanamycin A was prepared from 9 by the zinc acetate–ethyl trifluoroacetate method [to give 3,6′-bis(N-benzyloxycarbonyl)-1-epi-3″-trifluoroacetamidokanamycin A] followed by a regiospecific 1-N-acylation with (S)-4-benzyloxycarbonylamino-2-hydroxybutyryl group and successive deblocking.
  • Katsumi Nakamura, Tomoyuki Asai, Tamio Hara, Naoki Minorikawa, Tetsuo ...
    1983 年 56 巻 6 号 p. 1812-1816
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    In continuation of the preceding paper in this series, four derivatives of 1,2-dihydroxy-5,8-bis[2-(2-hydroxyethylamino)ethylamino]-9,10-anthracenedione: a positional isomer of mitoxantrone have been prepared to establish a relationship between the position of the hydroxyl groups on the A ring and antineoplastic activity against experimental leukemia L1210 in mice. Two compounds were found to be fairly active.
  • Akira Sugimori, Teruo Ogishima, Yoshiyuki Miyazawa, Ryo Hasegawa, Yoko ...
    1983 年 56 巻 6 号 p. 1817-1821
    発行日: 1983年
    公開日: 2006/06/27
    ジャーナル フリー
    The rate of photo-methoxylation of methyl 2-pyridinecarboxylate(1) in acidic methanol is accelerated by 4-substituted pyridines and their analogs, 4,4′-bipyridine and pyrazine. The photo-methoxylation of 1 is not promoted by triplet sensitizers, electron donors, or electron acceptors. Detailed analyses on the 1–4-pyridinecarbonitrile(3) system including wavelength dependence lead to a mechanism for the promotion via an excited complex formed from an excited 1 and 3 in the ground state.
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