Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 60 , Issue 6
Showing 1-50 articles out of 64 articles from the selected issue
  • Kumiko Iwai, Motomi Katada, Izumi Motoyama, Hirotoshi Sano
    1987 Volume 60 Issue 6 Pages 1961-1966
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Lattice dynamics in ferrocene derivatives, mono- and disubstituted acetyl-, carboxy-, and ethylferrocenes, tetrachloro(1,1′-diacetylferrocenato-O,O′)tin(IV) and tetrachlorobis(acetylferrocenato-O)tin(IV) have been studied by determining the temperature dependence of the recoil-free fraction and the thermal shift in the Mössbauer spectra. It was found that the lattice vibrations in acetyl- and carboxyferrocenes and adducts could be satisfactorily explained by assuming a harmonic oscillation model, while those of ethyl-substituted ferrocenes could not be interpreted by assuming harmonic vibrations.
  • Naotoshi Nakashima, Reiko Ando, Toyoki Kunitake
    1987 Volume 60 Issue 6 Pages 1967-1973
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Negatively-charged cyanine dyes are bound specifically to aqueous bilayer membranes of double-chain ammonium amphiphiles, as reflected in their absorption spectra. The quantum yield of the fluorescence emission of a trimethine-thiacyanine dye is remarkably enhanced (up to 0.64) when the dye is bound to crystalline bilayer membranes of certain double-chain ammonium amphiphiles. The fluorescence intensity diminished drastically with the liquid crystalline bilayers. Efficient energy transfer is noted from an oxacyanine to the thiacyanine dye in the crystalline membrane matrix. The efficiency decreases by the membrane phase transition to the liquid crystalline state. These results are discussed in terms of specific dye binding and concentration of dyes at the membrane surface.
  • Shoichi Shimizu, Choichiro Hirai
    1987 Volume 60 Issue 6 Pages 1975-1980
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The rates of the esterification of octanoic acid with 1-butanol catalyzed by macroreticular sulfonated ion-exchange resin in the presence of various organic solvents and water were measured by the use of a batch reactor. The solvent effects on the rate were investigated by applying the heterogeneous-pseudohomogeneous reaction mechanism. From these results, it was found that the effects can be quantitatively estimated by means of the magnitude of the equilibrium constants, Ksol(S), for the solvent-separated ion-pair formations, which are due to the interaction of the sulfo groups in the resin with the solvents. The correlations of the Ksol(S) value with the physical properties, μ and ε; the solvatochromic parameters, \boldmathπ*, \boldmathα, and \boldmathβ, and Gutmann’s parameters, ANE and DNB, have been examined by using linear regression analysis methods. The results of the correlations in which the protic solvents have been excluded suggest that the positions of the equilibria of solvent-separated ion-pair formations depend mainly on the electron-donor property of the solvents; that is to say, the solvents with a strong donor property diminish the number of un-ionized sulfo groups which act as catalytic species for the heterogeneous reaction.
  • Shoji Tanaka, Tsutomu Kumagai, Toshio Mukai, Tsunetoshi Kobayashi
    1987 Volume 60 Issue 6 Pages 1981-1983
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The electronic structures of 1,4-dihydropyrrolo[3,2-b]pyrrole and some of its alkyl derivatives were studied by means of He(I) photoelectron spectroscopy combined with the MNDO calculation and a first-order perturbation theoretical method. The first five bands of the parent pyrrolopyrrole are assigned, from the top, to the π5(au), π4(au), π3(bg), π2(bg), and σ(ag) bands respectively. The MO model, which explains well the spectral data, indicates that the nitrogen lone-pair electrons are mainly delocalized in the π4, π2, and π1 orbitals. The ionization potentials of the HOMO levels of these compounds, which are characterized by the large pz contributions from the α-carbons, are the lowest among the hitherto known π-electron-excessive heteroaromatic compounds. 1,4-Dihydropyrrolo[3,2-b]pyrrole is concluded to be the system with the most efficient π-electron-donating ability among 10π-electron systems.
  • Keiichiro Hatano, Kyoko Kawasaki, Sonono Munakata, Yoichi Iitaka
    1987 Volume 60 Issue 6 Pages 1985-1992
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The structure of one of the four atropisomers of tetrakis(o-cyanophenyl)porphyrin has been determined as the zinc complex by X-ray crystallographic methods. The five-coordinate zinc porphyrin with pyridine as the axial ligand also has a pyridine solvate in the crystal lattice. The conformation of the o-cyanophenyl rings is αβαβ as predicted previously. The two nitrogen atoms of the CN groups on the same side of the coordinated pyridine have close intramolecular contacts to pyridine at the van der Waals distance. However, the structural parameters, bond distances and angles of this molecule do not indicate distinct steric effects of the CN groups. Thermal atropisomerization among the four zinc porphyrin atropisomers occurs in solution. The quantitative composition of the atropisomers at equilibrium and the rates of the isomerization reaction have been determined with aliquots separated by TLC. A nonstatistical equilibrium distribution of the atropisomers suggests some mutual interactions among the CN groups. The slower isomerization rates of the zinc complexes compared to those of the free base have been discussed in connection with the molecular structure.
  • Hitoshi Oike, Yasushi Kai, Kunio Miki, Nobuo Tanaka, Nobutami Kasai
    1987 Volume 60 Issue 6 Pages 1993-1999
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The tricarbonylchromium complex of triple-layered [2.2]paracyclophane shows a reversible phase transition in the solid state from the monoclinic to the triclinic form at a temperature between −100 and −110°C. The monoclinic form crystallizes in the space group P21c, with a=15.095(6), b=9.950(3), c=15.641(5) Å, β=103.46(3)° (−95°C), and Z=4: The triclinic form belongs to the space group P\bar1, with a=15.037(5) Å, b=9.913(2), c=15.662(5) Å, α=89.41(3), β=104.51(3), γ=89.39(4)° (−160°C), and Z=4. In the triclinic crystal, two molecules are crystallographically independent. The crystal structures were solved by the direct method and then refined by the block-diagonal least-squares procedure to the R indices of 0.067 for 3530 (monoclinic form) and 0.079 for 6776 (triclinic form) observed reflections. No essential difference is found between the structures of the monoclinic-form molecule and the two triclinic-form molecules. The interlayer distance between the upper-layer benzene ring coordinated to the Cr(CO)3 group and the middle-layer benzene ring is unusually shorter than the corresponding distance between the middle- and lower-layer benzene rings. No bond alternation is found in the upper-layer benzene ring, unlike as in the tricarbonyl(benzene)chromium complex and the (tricarbonyl)chromium complex of double-layered [2.2]paracyclophane. The phase transition of the crystal can be explained by a slight change in the molecular packing.
  • Michio Matsumura, Hideyuki Ohnishi, Koji Hanafusa, Hiroshi Tsubomura
    1987 Volume 60 Issue 6 Pages 2001-2003
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The photocatalytic activity of platinum-loaded CdS powder in sulfite solutions declined by illumination over 200 h, and became half the initial activity at 600 h. By addition of small amount (2 mM) of ethylenediaminetetraacetic acid (EDTA) to the solution, however, the photocatalyst was guarded from deterioration. The effect of EDTA is to prevent the platinum part of photocatalyst from the impurity metal deposition by forming stable metal-EDTA complexes in the solution. The reactivities of sulfite ions, EDTA, and metal-EDTA complexes on illuminated CdS are examined electrochemically by use of CdS-sinter electrodes.
  • Noriyuki Mizoguchi
    1987 Volume 60 Issue 6 Pages 2005-2010
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The McWeeny theory for calculating magnetic properties of conjugated hydrocarbons is studied from a graph-theoretical point of view. Imaginary bond–bond polarizability is expressed in terms of characteristic polynomial. The expression clarifies the dependence of imaginary bond–bond polarizability on the structure. It is shown that the expression enables one easily to derive the equations for the quantity proved in two previous papers. The characteristic polynomial expression for imaginary bond–bond polarizability is rewritten in Coulson’s integral form. The rules for London susceptibility and for ring current are proved from the integral expression.
  • Yasukiyo Ueda
    1987 Volume 60 Issue 6 Pages 2011-2017
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Five paraffins (C30–C44) and three linear compounds with polar end-groups, such as hydroxyl, methyl-ester, and carboxyl groups, were deposited on the cleavage surface of an alkali halide crystal in vacuo. Paraffin films deposited on the substrate took the same crystal structure and molecular orientation, independent of the number of carbon atoms in the chain. In the case of derivatives, the morphology and orientation of the crystals, however, differed with the end-groups. The (110) planes of paraffins, alcohol, and methyl-ester crystals were oriented parallel to the substrate (001) plane, and their c-axes were parallel to the [110] direction of the substrate crystal. On the other hand, the (001) plane of the acid crystal lay parallel to the substrate surface, so that the c-axis of the crystal was oblique to the substrate surface. The epitaxial growth of linear molecules with different end-groups was explained by the difference in the interaction between the end-groups and the substrate.
  • Jie Tang, Tohru Kamo, Muneyoshi Yamada, Yozo Ohshima, Akira Amano
    1987 Volume 60 Issue 6 Pages 2019-2022
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The title reaction was investigated at room temperature and under pressures ranging from 133 to 2660 Pa. 1-Butanethiol, butane, and 1-butene were the main products. In the reaction with deuterium atom, dibutyl disulfide and 1-butanethiol were not deuterated, while butane was monodeuterated. The following mechanism was proposed to account for the product composition and its pressure dependency as well as the deuterium labeling of the products. C4H9SSC4H9+D· → n-C4H9SD +n-C4H9S·, n-C4H9S· +D· → n-C4H9SD*, n-C4H9SD*+M → n-C4H9SD, n-C4H9SD*Δ′-C4H8+HDS, n-C4H9SD*n-C4H9· +DS·, n-C4H9· +D· → n-C4H9D, n-C4H9· +D· → Δ′-C4H8+HD.
  • Hajime Karatani
    1987 Volume 60 Issue 6 Pages 2023-2029
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The effects of water-soluble polymers(WSPs), such as bovine serum albumin(BSA) and polyethylenimine(PEI), on chemiluminescence(CL) in an aqueous solution have been studied. The CL emission, particularly in the initial stage of the CL reaction, was strongly enhanced by increasing the concentrations of these WSPs. This was attributed to the acceleration of the chemical reactions prior to the formation of the light-emitting species. BSA was also peculiar in that it could enhance CL under neutral pH conditions. It was suggested that these WSPs offered hydrophobic and basic microenvironments well suited to the CL reaction.
  • Tadashi Hara, Kazuhiko Tsukagoshi
    1987 Volume 60 Issue 6 Pages 2031-2035
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Osmium(VIII) was found by the authors to show extremely sensitive catalytic activity for the 1,10-phenanthroline–hydrogen peroxide chemiluminescence system. By optimizing the measurement conditions, 3.2×10−11–1.3×10−8 mol dm−3 osmium(VIII) could be determined by chemiluminescence flow-injection analysis with a detection limit of 0.4 pg. The method for the determination of protein was established; it was based on the lowering of the catalytic activity of osmium(VIII) attributable to the complex formation between osmium(VIII) and protein. Similar calibration curves were obtained for bovine serum albumin, human serum albumin, and human serum γ-globulin under the optimum conditions for the determination of protein. According to the method, 5.0×10−6–1.0×10−3 g dm−3 protein could be determined with a detection limit of about 250 pg and with a coefficient of variation of 2.9% (n=10) for a 1.0×10−4 g dm−3 protein solution.
  • Kazuharu Nakagawa, Kayoko Amita, Hifumi Mizuno, Yoshihisa Inoue, Tadao ...
    1987 Volume 60 Issue 6 Pages 2037-2040
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Lanthanoid(III) picrates (Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, and Yb) were prepared from picric acid and the corresponding lanthanoid carbonates in good yields. Combustion analyses, ICP emission analyses, and UV spectrophotometry have shown that the light lanthanoid picrates, i.e. Ln=La–Gd, are all undecahydrates, while the heavy ones, Dy and Yb, are octahydrates. An examination by TG-DTA has revealed that these hydrates, being fairly stable in air at ambient temperature, are quite labile to give partially or completely dehydrated samples upon drying under vacuum, in a desiccator, and/or at elevated temperatures just above 30°C.
  • Masumi Ushio, Yoshihiro Sumiyoshi
    1987 Volume 60 Issue 6 Pages 2041-2045
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The wetting of the Al2O3 substrate by liquid silver was investigated by means of the sessile-drop technique in an atmosphere of argon. An empirical relation was established between the contact angle and the temperature or surface tension of the liquid drop by the use of the diameter and the height of the sessile drop. The contact angle was constant as the time increased while it decreased linearly with the increase in the temperature. The variation in the contact angle with the temperature is correlated with the surface tension of the sessile drop. The critical surface tension (γc) of Al2O3 is 361 dyn cm−1, while the surface tension of liquid silver at 0 K is 790 dyn cm−1.
  • Masunobu Maeda, Masato Hayashi, Shoichiro Ikeda, Yoshiaki Kinjo, Kanam ...
    1987 Volume 60 Issue 6 Pages 2047-2052
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The dissociation constants of ammonium ion were determined at 25°C by potentiometry with glass and ammonium-ion-selective electrodes in artificial seawaters at various salinities (25–45\ extperthousand) and in concentrated sodium chloride aqueous solutions (0.72–3.2 mol kg−1). The activity coefficients of ammonia in sodium chloride solutions of the same ionic strengths as those of the artificial seawaters and in the concentrated sodium chloride solutions, which were used for the theoretical estimation of the dissociation constants, were measured by a transpiration method. The dissociation constants were theoretically evaluated in terms of the ionic interaction model developed by Pitzer and co-workers, and compared with the experimental ones. The predicted dissociation constants showed a good agreement with the observed ones.
  • Shin-ichi Ishiguro, László Nagy, Hitoshi Ohtaki
    1987 Volume 60 Issue 6 Pages 2053-2058
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Mixed ligand complexation of copper(II) with bromide ions and 2,2′-bipyridyl (bpy) has been calorimetrically studied in N,N-dimethylformamide (DMF) containing 0.16 mol dm−3 (C2H5)4NClO4 at 25°C. Complexation of the metal ion with 2,2′-bipyridyl has been also studied in the same solution. The calorimetric titration curves obtained were satisfactorily explained in terms of formation of the mononuclear [CuBrp(bpy)q](2−p)+ (denoted as (1pq)) complexes such as (101), (102), (103), (111), (121), and (112), and their formation constants and enthalpies were determined. The mixed ligand (111), (112), and (121) complexes are quite stable and yielded to a large extent in the DMF solution. Electronic spectra of these complexes have been measured in DMF over the range 400–1500 nm. The thermodynamic quantities of formation and electronic spectra of the complexes thus obtained are discussed in connection with the coordination structure of the complexes in DMF. The formation of the five-coordinate [Cu(bpy)2(dmf)]2+ and [CuBr(bpy)2]+ complexes is suggested in the DMF solution as well as in crystal.
  • Isao Sanemasa, Youko Akamine
    1987 Volume 60 Issue 6 Pages 2059-2066
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Formation constants of the following aromatic hydrocarbons with α-,β-, and γ-cyclodextrin(CyD) were determined in aqueous medium at 25°C in the presence of excess CyD : benzene, toluene, ethylbenzene, propylbenzene, isopropylbenzene, (o-, m-, and p-)xylene, and (1,2,3-, 1,2,4-, and 1,3,5-)trimethylbenzene. The technique used to study association between host(CyD) and guest (hydrocarbon) is based on the facts that the guest molecules can be driven out to gaseous phase by introducing an inert gas at a constant flow rate into the aqueous solution and that the volatilization rate of guest decreases with increasing association with the host in the aqueous solution. The 1 : 1 and 2 : 1 (host : guest) formation constants were evaluated. As a measure of hydrophobicity of guest molecules, the free energy change of dehydration derived from Henry’s law constant was used. Based on hydrophobicity and a host-guest spatial-fitting model, the formation constants have been discussed.
  • Susumu Takamoto, Chikako Enkaku
    1987 Volume 60 Issue 6 Pages 2067-2071
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Various computer processes to determine all parent ligand graphs, simple cage graphs, and donor-atomic graphs for the octahedral coordination are described in order to design new sexidentate ligands. A complex ligand graph is represented by a numeral comprising of 12 figures, each of which indicates the code of a unit graph of six kinds placed on 12 edges of an octahedron. Then, 1055 parent ligand graphs, excluding chiral isomers, are selected from 612 permutations of the complex ligand graphs. A simple cage graph is produced by fusing a pair of adjacent lines around every point of an octahedral graph; 102 kinds of simple cage graphs, excluding chiral isomers, have been obtained. Another more practical method for ligand design has been proposed by starting from 62 donor-atomic graphs.
  • Hajime Aoyama
    1987 Volume 60 Issue 6 Pages 2073-2077
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The substitution reaction of 5-substituted 2,4-bis(trimethylsilyloxy)pyrimidines with 3,5-bis(O-p-chlorobenzoyl)-2-deoxy-α-D-ribofuranosyl chloride was investigated. In the presence of p-nitrophenol, β anomers were formed stereoselectively, whereas the addition of organic bases brought forth stereoselective formation of α anomers. Stereoselectivity of the reaction depends on the substituents at 5-position of disilylpyrimidines, additives, and the concentration of each reagent. The α and β anomers of 5-substituted 2′-deoxy-uridines were synthesized through the deacylation of α and β anomers of 5-substituted 3′,5′-di-O-(p-chlorobenzoyl)-2′-deoxyuridines.
  • Kazuaki Kanai, Seiichiro Ogawa, Tetsuo Suami
    1987 Volume 60 Issue 6 Pages 2079-2083
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    7′-Phenylfortimicin A and 7′-phenyl-6′-epifortimicin A have been synthesized by condensation of newly prepared 1-O-acetyl-2,6-bis(2,4-dinitrophenylamino)-2,3,4,6,7-pentadeoxy-7-phenyl-L-lyxo-heptopyranose and -D-ribo-heptopyranose, respectively, with 2,5-di-O-benzoyl-1,4-bis[N-(methoxycarbonyl)]fortamine B, followed by deprotection.
  • Masao Okubo, Toshiki Tsutsumi, K\={o}ji Matsuo
    1987 Volume 60 Issue 6 Pages 2085-2090
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    In the electron transfer initiated fifteen reactions of five organomagnesium reagents, a semiquantitative relationship between the product distribution and the electron-donating and -accepting abilities (EDA and EAA) of reactants was obtained. The EDA was estimated by cyclic voltammetry of oxidation peak potentials of reagents and/or by the product distribution in their reactions, the decreasing order of EDA being: ArMgBr>ArSMgBr>ArNHMgBr>ArN(MgBr)2>ArOMgBr. The EAA of six quinones, eight nitroarenes, eleven aromatic ketones and an imine, and five azoxyarenes were similarly estimated by their reduction potentials (redox) in THF. The values of differences between the oxidation peak and reduction potentials were taken as an estimate of the relative efficiency of electron transfer, and were correlated to the distribution of normal (addition, condensation, replacement, and azoxy-deoxygenation) and abnormal (radical) products. Some exceptional cases were explained by modifying EDA and/or EAA based on the effect of coordination of substrate’s oxygen to reagent’s Mg atom.
  • Azuma Watanabe, Yasuo Fukagawa, Tomoyuki Ishikura, Takeo Yoshioka
    1987 Volume 60 Issue 6 Pages 2091-2099
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The stabilizing effect of the 6-methoxyl or 6-hydroxyl substituent on dehydropeptidase I sensitivity of PS 5 was examined by a new total synthesis of 6-methoxy-epi-PS 5 and 6-hydroxy-epi-PS 5 from dimethyl benzyloxycarbonylaminomalonate. The Wittig reaction of α-(t-butoxycarbonyl)propylidenetriphenylphosphorane with a pyrrolidine derivative predominantly afforded a trans-α,β unsaturated ester, which was epoxidated, N-deprotected and cyclized to give a bicyclic carbapenam with a C-6 hydroxyl group. After the 6-hydroxyl group was methylated, the 2-(acetamido)ethylthio side chain was introduced at C-3 of the carbapenam by benzeneselenenylation of the geminal diester, followed by elimination of the seleninyl group. The resulting carbapenam was converted to 6-methoxy-epi-PS 5. Furthermore, 6-hydroxy-epi-PS 5 was synthesized by the use of tetrahydropyranyl and trimethylsilyl ethers for protection of the 6-hydroxyl group in a process similar to that for synthesis of 6-methoxy-epi-PS 5.
  • Makoto Tamaki, Michiaki Takimoto, Ichiro Muramatsu
    1987 Volume 60 Issue 6 Pages 2101-2104
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    In order to investigate the structure-activity relationship of the “gratisin”-related peptide, cyclo(–Val–Orn–Leu–D-Phe–Pro–D-Tyr–)2 (GR-I), its two analogs, cyclo(–Val–Orn–Leu–D-Ala–Pro–D-Tyr–)2 (6a) and cyclo(–Val–Orn–Leu–D-Phe–Pro–D-Ala–)2 (6b), were synthesized. The CD spectra of these synthetic peptides in an aqueous solution were similar to that of GR-I, indicating that these peptides have similar conformations in an aqueous solution. The activity of 6b was half that of GR-I, whereas 6a did not show any antibiotic activity. These results indicated that the phenyl group of the D-Phe residue preceding the Pro residue is essential for exhibiting the activity, while the p-hydroxyphenyl group of the D-Tyr residue following the Pro residue is not essential.
  • Katsuhiro Saito
    1987 Volume 60 Issue 6 Pages 2105-2109
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Reactions of tropone tosylhydrazone sodium salt with dimethyl and diethyl acetylenedicarboxylate gave dimethyl and diethyl 1H-1,2-benzodiazepin-3,4-dicarboxylate, respectively. The same reactions, but using ethyl acetylenecarboxylate and 3-butyn-2-one, afforded ethyl 1H-1,2-benzodiazepin-4-carboxylate and 4-acetyl-1H-1,2-benzodiazepine, respectively, accompanied by 8-azaheptafulvene derivatives derived from the sodium salt and the acetylene derivatives, and p-toluenesulfinic esters formed from p-toluenesulfinic acid and the acetylene derivatives. Reactions of the sodium salt with ethyl 2-butynoate gave the corresponding sulfinic ester but afforded no diazepine derivative.
  • Takanori Suzuki, Chizuko Kabuto, Yoshiro Yamashita, Toshio Mukai
    1987 Volume 60 Issue 6 Pages 2111-2115
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The crystal structure of TTF·BTDA–TCNQ complex was determined by an X-ray diffraction method. The crystals are monoclinic, space group P21n with a=9.660(1), b=7.231(1), c=14.628(2) Å, β=91.31(1)°, and Z=2. The structure was solved by the direct method and refined by the block-diagonal least-squares method to give an R value of 0.040 for non-zero 2620 reflections. The complex is nonionic and the molecules form equally spaced mixed stacks along the b axis. These stacks are connected by strong transverse interactions resulting in a three-dimensional structure. BTDA–TCNQ molecules make cavities by S–N≡C interactions in which TTF molecules are included. This complex is not a simple CT complex with mixed stacks but rather the one with some inclusion behavior.
  • Tadaaki Nishihama, Takeyoshi Takahashi
    1987 Volume 60 Issue 6 Pages 2117-2125
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Base-catalyzed autoxidation of a triterpene ketone, friedelin, in the presence of potassium t-butoxide gave four products, and their structures and formation mechanism were investigated. The common intermediate to these compounds was suggested to be 4-hydroperoxyfriedelan-3-one, not friedelane-2,3-dione. 3-Oxafriedel-1-ene-2-carboxylic acid was a dehydration product of the main product, 2-hydroxy-3-oxafriedelane-2-carboxylic acid.
  • Tamejiro Hiyama, Kazuhiro Kobayashi, Kiyoharu Nishide
    1987 Volume 60 Issue 6 Pages 2127-2137
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Alkanoate esters are found to couple with various nitriles to give (Z)-3-amino-2-alkenoates in good yields with the aid of a magnesium amide prepared by the reaction of ethylmagnesium bromide and diisopropylamine. The C–C bond forming reaction was applied to (2S,3S)-2,3-(cyclohexylidenedioxy)butanenitrile and the resulting adduct was successfully converted into N-benzoyl-L-daunosamine in 41% overall yield through a sequence of functional group manipulation; acetylation, hydrogenation, hydrolysis and benzoylation, lactonization and finally reduction. By the similar process, (2R,3S)-2,3-(cyclohexylidenedioxy)butanenitrile was transformed to N-benzoyl-L-acosamine in 25% overall yield.
  • Tamejiro Hiyama, Haruhito Oishi, Yukari (nee Kusano) Suetsugu, Kiyohar ...
    1987 Volume 60 Issue 6 Pages 2139-2150
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Two new routes to 4-amino-2(5H)-furanones are disclosed. The one is based on the reaction of a magnesium enolate of t-butyl acetate or propionate with O-protected cyanohydrins followed by acid-treatment which effects hydrolysis of the ester group, deprotection, olefin isomerization and lactonization all in a single operation. The other is base-induced ringclosure of α-acyloxy nitriles. The two methods are applied to construction of the carbon framework of an antitumor antibiotic basidalin.
  • Mitsuhiro Kinoshita, Hitoshi Takami, Masato Taniguchi, Tetsuro Tamai
    1987 Volume 60 Issue 6 Pages 2151-2161
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    3-Deoxy-1,2-O-isopropylidene-3-C-methyl-α-D-allofuranose was stereoselectively converted into 3,5-dideoxy-4-O-(methoxymethyl)-3,5-di-C-methyl-6-O-pivaloyl-L-talose ethylene dithioacetal (31) via 3,5-dideoxy-4-O-(methoxymethyl)-3,5-di-C-methyl-L-talopyranuro-6,2-lactone ethylene dithioacetal (24) in 10 steps (23.6% overall yield). Desulfurization [Raney Ni W-4, 92% yield] of 31 followed by three-step transformation (91% yield) afforded 2,4,6-trideoxy-5-O-(diethylisopropylsilyl)-3-O-(methoxymethyl)-2,4-di-C-methyl-L-altrose, which was olefinated by using methyl (2E,4E)-6-(dimethoxyphosphinyl)-2,4-hexadienoate twice to give the target compound, all-trans-hexaenal 4 (12 steps, 38.6% overall yield from 31).
  • Kazuo Mukai, Satoshi Yokoyama, Kazuyuki Fukuda, Yuichi Uemoto
    1987 Volume 60 Issue 6 Pages 2163-2167
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The second-order rate constants ks for the reaction of 10 kinds of tocopherol (vitamin E) model compounds with stable phenoxyl radical in ethanol have been measured at 25.0°C, using a stopped-flow spectrophotometer, as a model reaction of tocopherols with unstable free radicals (ROO·, RO·, and HO·) in biological systems. The absolute ks values of α-, β-, γ-, and δ-tocopherol models are similar to or slightly smaller than those of the corresponding tocopherols having a long-phytyl-chain. The relative ks values (α: β: γ: δ=100 : 53 : 50 : 24), that is, relative antioxidant activities, of α-, β-, γ-, and δ-tocopherol models are in good agreement with those (100 : 44 : 47 : 20) of α-, β-, γ-, and δ-tocopherols. The antioxidant activities of tocopherol models having two alkyl substituents, such as methyl, ethyl, isopropyl, and t-butyl groups, at ortho positions of OH group are similar to each other, suggesting that the effect of steric hindrance on the reaction rate is small. 5,7-Dimethyltocol model has quite similar rate constants with those of β- and γ-tocopherol models, whereas δ-tocopherol model is only ca. 24% as reactive as α-tocopherol model and tocol model is only ca. 10% as reactive as α-tocopherol model. The result indicates that the rate constants increase as the total electron donating capacity of the alkyl substituents at aromatic ring increases. For the tocopherol models logks was found to correlate with Σσ+ substituent constants with a ρ+ value of −1.0.
  • Kiyoshi Yamauchi, Mitsuyoshi Hihara, Masayoshi Kinoshita
    1987 Volume 60 Issue 6 Pages 2169-2172
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    2-Methoxyethoxymethyl (MEM) and 2-(trimethylsilyl)ethoxymethyl (SEM) groups were used to protect the sn-3-OH of optically active glycerols in the synthesis of 1,2-di-O-octadecyl-sn-glycero-3-phosphatidylcholine. Both MEM and SEM protective groups had advantages of a classical benzyl group by virtue of (i) the facile preparation of 1,2-O-isopropylidene-3-O-(2-methoxyethoxymethyl)-sn-glycerol and its sn-3-O-SEM analog as starting materials and (ii) the rapid demasking of the MEM and SEM moieties in lipid precursors, especially by means of titanium tetrachloride.
  • Sigeru Torii, Tsutomu Inokuchi, Sadahito Takagishi, Hirofumi Horike, H ...
    1987 Volume 60 Issue 6 Pages 2173-2188
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Exquisite use of electrogenerated acid (EG acid) in the silicon-mediated acid-catalyzed reactions; e.g., aldol reactions, allylations, cyanations, and hydride additions is described. The aldol reaction of acetals 1 with enol trimethylsilyl ethers 3 and 1,2-bis(trimethylsiloxy)alkenes 4 gives the corresponding adducts 5 and 6, respectively. The reaction proceeds smoothly with EG acid derived from perchlorate salts such as LiClO4, n-Bu4NClO4, and Mg(ClO4)2 in dichloromethane using platinum electrodes. The amount of electricity required to complete the reaction implies a cationic process which is mediated by the trimethylsilyl moiety. This aldol reaction is further developed with unprotected carbonyl compounds 2 with 3, giving the trimethylsilyl ethers of the adducts 7. Further utility of this EG acid as a catalyst for a chain reaction is exemplified by the successful application in the following conversions: (1) The allylation of acetals 1 with allyltrimethylsilane (8) to give 9, (2) the cyanation of acetals 1 and unmasked 2 with trimethylsilyl cyanide (10) to give 11, 12, and 13, and (3) the hydride addition of acetals 1 with triethylsilane (14) to give 15.
  • Kin-ichi Tadano, Chiyoko Fukabori, Masayuki Miyazaki, Hiroshi Kimura, ...
    1987 Volume 60 Issue 6 Pages 2189-2196
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Diisobutylaluminium hydride reduction of D-glucose-derived chiral synthon, (1R,6R,8R,9R)-8,9-isopropylidenedioxy-7-oxabicyclo[4.3.0]non-4-en-3-one (1), gave a 7:1 mixture of (1R,3S,6R,8R,9R)- and (1R,3R,6R,8R,9R)-8,9-isopropylidenedioxy-7-oxabicyclo[4.3.0]non-4-en-3-ol, (2) and (2′). Introduction of cis-diol to the double bond of 3-O-acetyl derivatives of 2 and 2′ by osmium tetraoxide oxidation provided the diastereomeric mixture of (1R,3S,4R,5S,6S,8R,9R)-3-acetoxy-8,9-isopropylidenedioxy-7-oxabicyclo[4.3.0]nonane-4,5-diol (5) and (1R,3R,4S,5R,6S,8R,9R) diastereomer. Compound 5 was transformed to optically active pseudo-β-L-allopyranose effectively via (1R)-1-[(1S,2S,3S,4R,5S)-3,4,5-tris(benzyloxy)-2-hydroxycyclohexyl]-1,2-ethanediol (9). Cyclohexanecarbaldehyde formed by glycol cleavage of 9 was treated with methanesulfonyl chloride and reduced with lithium aluminium hydride to give (3S,4R,5S)-3,4,5-tris(benzyloxy)-1-cyclohexene-1-methanol (13). Compound 13 was efficiently converted to pseudo-α-D-mannopyranose pentaacetate by stereoselective hydroboration as a key reaction. The Wharton reaction of (1R,4S,5S,6S,8R,9R)-4,5-epoxy-8,9-isopropylidenedioxy-7-oxabicyclo[4.3.0]nonan-3-one derived from 1 gave(1R,5R,6S,8R,9R)-8,9-isopropylidenedioxy-7-oxabicyclo[4.3.0]non-3-en-5-ol, into which (3S,4S)-diol was stereoselectively introduced by oxidation with osmium tetraoxide.
  • Masahiro Imoto, Hiroyuki Yoshimura, Michiharu Yamamoto, Tetsuo Shimamo ...
    1987 Volume 60 Issue 6 Pages 2197-2204
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    2,2′-N:3,3′-O-Tetrakis[(R)-3-hydroxytetradecanoyl]-β(1-6)-D-glucosamine disaccharide 1,4′-bis(phosphate) and its dephospho derivatives were synthesized. The bisphosphate prepared was shown to be identical with a natural biosynthetic precursor of lipid A which corresponds to the lipophilic part of lipopolysaccharide (LPS) in bacterial cell wall. The synthetic bis- and monophosphates exhibited many of typical endotoxic activities of LPS. Consequently, this work established the chemical structure of the biosynthetic precursor of lipid A and elucidated the fundamental structure required for the expression of these activities.
  • Masahiro Imoto, Hiroyuki Yoshimura, Tetsuo Shimamoto, Nobuki Sakaguchi ...
    1987 Volume 60 Issue 6 Pages 2205-2214
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Chemical syntheses are described of polyacylated β(1→6) glucosamine disaccharide 1,4′-bis(phosphate), which corresponds to the proposed structure of E. coli lipid A, and of its dephospho derivatives. The synthetic bisphosphate proved to be identical with the corresponding natural specimen. The chemical structure of lipid A was thus established.
  • Yutaka Hirata, Masashi Date, Yukiko Yamamoto, Akira Yamauchi, Hideo Ki ...
    1987 Volume 60 Issue 6 Pages 2215-2219
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    In order to clarify the membrane phenomena in an amphoteric membrane, four different experiments were carried out in a simple electrolyte-amphoteric membrane system. The ion transport numbers obtained from the membrane potential and electrodialysis were approximately in agreement with each other. It was indicated that the transport numbers strongly depended on the ionic valence in electrolyte solution. The membrane permeability coefficient representing the dynamic behavior of ion within membrane was evaluated in terms of membrane potential, transport number, and membrane conductance. In addition, the ionic concentrations within membrane equilibrated with outer electrolyte solution were measured to obtain the mobilities within membrane. The membrane phenomena were discussed on basis of the present experimental results.
  • Kosaku Suga, Koushi Maemura, Masamichi Fujihira, Shigeru Aoyagui
    1987 Volume 60 Issue 6 Pages 2221-2226
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    ESR spectra of duroquinone anion radical (DQ), methyl viologen cation radical (MV+), and 5,10-dimethyl-5,10-dihydrophenazine cation radical (DMPZ+) were measured in various aqueous surfactant solutions. The line width of each peak of the ESR spectra for DQ in cationic and anionic surfactant solutions showed a quadratic dependence on the total nuclear quantum number, Mmi (i=1 to 12), of methyl protons of DQ. The rotational correlation times, τc, of DQ determined from these dependences, were 10−9–10−8 s in cationic surfactant (dodecyl-, tetradecyl-, and hexadecyltrimethylammonium bromide) solutions, and 10−10–10−9 s in nonionic surfactant (Triton X-100) solution. ESR spectra of MV+ and DMPZ+ in anionic surfactant (sodium dodecyl sulfate; SDS) solution showed anomalous patterns as not exhibiting the hyperfine splittings due to the nitrogen nucleus. These anomalies were explained by the more significant broadening of the outer peaks due to nitrogen splitting compared with the broadening of the central peaks corresponding to the nuclear quantum number of nitrogen, MN=mN1+mN2=0. From these results, the rotational correlation time for DMPZ+ in SDS solution was estimated as about 10−10 s.
  • Yutaka Saito, Mitsuko Satouchi, Masaki Mifune, Takaaki Tai, Junichi Od ...
    1987 Volume 60 Issue 6 Pages 2227-2230
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The catalase-like activity of anion-exchange resins (Amberlite IRA 900) modified with various metalloporphyrins in the acceleration of reaction (1) was evaluated by efficiency in color reaction (2) based on dye formation:
    H2O2+CH3OH\oversetcatalase\ ightharpoonup2H2O+HCHO (1)
    HCHO+4-amino-3-hydrazino-5-mercapto-1,2,4-triazole+KIO4\oversetOH\ ightharpoonupDye(λmax=550 nm). (2)
    Amberlite IRA 900 modified with Mn3+–tetrakis(sulfophenyl)porphine (MnTPPSr) was found to exhibit the highest catalase-like activity among the resins tested and was applied as a mimesis of catalase to the determination of hydrogen peroxide by the use of reactions (1) and (2). The molar absorption coefficient for hydrogen peroxide was found to be 2.37×104 mol−1 dm3 cm−1, which is larger than twice that in the control catalase method (0.97×104 mol−1 dm3cm−1). Interferences by common foreign substances tested were found to be small. MnTPPSr gave a better result than catalase in the determination of hydrogen peroxide.
  • Hidekazu Doe, Kenichi Wakamiya, Toyokichi Kitagawa
    1987 Volume 60 Issue 6 Pages 2231-2235
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The stability constants of alkaline-earth metal chlorides, MCl+ (M2+=Ca, Sr, Ba), were determined by conductometric and potentiometric measurements in methanol. The conductometric study was made at 5, 15, 25, 35, and 45°C; the potentiometric study was at 25°C. The formation of MCl2 was neglected in the conductometric study, while in the potentiometric study it was taken into account, though it was too slight to determine a reliable value of the stability constant of MCl2. The stability constants of MCl+, K1, determined by conductometric measurements were compared with the previous conductometric results of the same metal(II) perchlorates, K1A. The magnitudes of K1 and K1A increase in the orders Ca \simeqSr<Ba and Ca<Sr<Ba, respectively. K1 is larger than K1A for calcium and strontium, though the K1 and K1A values for barium are similar to each other; that is, the degree of such an increase in K1A is larger than that in K1. Both enthalpy and entropy changes determined by conductometric measurements were positive for all the chlorides and perchlorates. However, the enthalpy changes of the chlorides were 1.2–1.4 times as large as those of the perchlorates. On the other hand, the K1 from potentiometry was smaller for every chloride and also increased more steeply (in the order Ca<Sr<Ba) than that from conductometry. Therefore, the difference of K1 between conductometry and potentiometry decreases in going from Ca to Ba.
  • Kaoru Fujimoto, Masahiko Kajioka
    1987 Volume 60 Issue 6 Pages 2237-2243
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Fischer–Tropsch synthesis on supported ruthenium catalysts were operated successfully in the slurry phase, using ethyl cyclohexane solvent, in spite of the high selectivity of waxy products. Titania, fumed silica, and Nb2O5 were found to be excellent carriers for ruthenium. A Ru/SiO2 catalyst yielded a hydrocarbon product with the rate as high as 600 mg(g-cat)−1h−1 at 240°C and 40 bar. The optimum metal loading was 2% by weight. Calcination of the catalyst precursor at 300°C or above caused a marked decrease in the metal dispersion, which was essential for the high catalytic activity and chain-growth ability. The maximum chain-growth probability obtained on a calcined Ru/Al2O3 catalyst was 0.94.
  • Hitoshi Funayama, Takuo Sugawara
    1987 Volume 60 Issue 6 Pages 2245-2249
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    To determine the absolute light intensity (including the reflective, scattered, and incident light intensity) in a UV-transmitting and UV-dispersive fluoro polymer tube, a new chemical actinometer, DPOF system, was introduced which was composed of dilute potassium tris(oxalato)ferrate(III), 0.03 mol m−3; 1,10-phenanthroline, 0.135 mol m−3; and potassium oxalate, 1.5 mol m−3. The overall light intensity was determined with a simple procedure based on a precise analysis of the photochemical kinetics of a DPOF system. The absolute intensities at 366 nm in the UV-transmitting and UV-dispersive Teflon FEP and Folaflon PVdF tubes were detected to be higher than that in a fused-silica tube of similar size while the incident light intensities in the former tubes were always lower than that in the latter. In addition, the dispersive effect of a Teflon FEP tube was rather independent of the wall thickness and the tube diameter under the experimental conditions studied, owing to its high dispersibility of light. The dispersive effect was much more remarkable for the Folaflon PVdF tube. The property of light transmission with dispersion, with the characteristic of antifouling, would make the fluoro polymer tubes useful for novel photoreactors in various areas.
  • Tatsuo Erabi, Yoshiharu Yamashita, Kumiko Nishimura, Masanori Wada
    1987 Volume 60 Issue 6 Pages 2251-2252
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    A spectroelectrochemical technique has been used for redox study of cytochrome c′ in chromatophores in the presence of Toluidine Blue O as a mediator. The midpoint potential of cytochrome c′ thus determined was 0 mV (n=1) at pH 7.0, which agreed well with the value determined by redox titration.
  • Satoru Nakashima, Motomi Katada, Izumi Motoyama, Hirotoshi Sano
    1987 Volume 60 Issue 6 Pages 2253-2254
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    1′,1'″-Dimethyl-, 1′,1'″-dipentyl-, 1′,1'″-dihexyl-, and 1′,1'″-didecylbiferrocene were synthesized and Mössbauer spectroscopic measurements of their monocation salts were carried out at various temperatures in order to know the mixed-valence states. Effects of alkyl substituent on the valence states of iron atoms in the monocation salts of 1′,1'″-dialkylbiferrocenes are discussed.
  • Kunio Mochida, Kenji Kojima, Yasuhiro Yoshida
    1987 Volume 60 Issue 6 Pages 2255-2256
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Calcium atoms have been inserted into C–H bonds of heterocyclic (furans and thiophene) and alicyclic compounds (cyclohexanes and cyclopentane) to give the corresponding organocalcium hydrides. The organocalcium hydrides thus produced reacted with trimethylchlorosilane to give trimethylsilyl-substituted heterocyclic and alicyclic compounds, and a reduced product (trimethylsilane).
  • Kazuaki Sukata
    1987 Volume 60 Issue 6 Pages 2257-2258
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Potassium and sodium cyanide impregnated on Amberlite XAD resin were found to be effective for converting alkylsilyl chloride to the corresponding alkylsilyl cyanide under mild conditions.
  • Morio Asaoka, Keiji Ishibashi, Wataru Takahashi, Hisashi Takei
    1987 Volume 60 Issue 6 Pages 2259-2260
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Dienol silyl ethers of various 2-cyclohexenones reacted with 4-methyl-3-penten-2-one(mesityl oxide) or methyl acrylate in the presence of Lewis acid to give bicyclo[2.2.2]octanes in moderate yields.
  • Hajime Takahashi, Teruji Sasaki, Masaaki Ito
    1987 Volume 60 Issue 6 Pages 2261-2262
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    New flavonoid compounds, 3,5-dihydroxy-6,7-methylenedioxyflavanone, 2′,5-dihydroxy-6,7-methylenedioxyisoflavone, and 5-hydroxy-6,7-methylenedioxyflavone were isolated from sugarbeet roots infected with Rhizoctonia solani.
  • Daiyo Terunuma, Makoto Nakamura, Eiji Miyazawa, Hiroyuki Nohira
    1987 Volume 60 Issue 6 Pages 2263-2264
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    A new silaspiro compound, i.e., spiro[silacyclobutane-1,9′-[9H-9]silafluorene](1) was synthesized in 75% yield. It was found that the pyrolysis of 1 at 650°C under a reduced pressure gave a head-to-tail silaethene dimer in 15% yield. Copyrolysis of 1 in the presence of benzophenone gave 1,1-diphenylethene and a siloxane oligomer in 50 and 30% yield, respectively.
  • Keiichi Ohno, Hiroatsu Matsuura
    1987 Volume 60 Issue 6 Pages 2265-2267
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The gas-phase infrared spectra of ethylidynephosphine CH3C≡P and its perdeuteride CD3C≡P were measured in the 50–400 cm−1 region with a resolution of 0.12 cm−1. The molecular constants for the ν8±1 and 2ν80–ν8±1 bands were determined by the P,RQK branch analysis.
  • Jun-ichi Aihara
    1987 Volume 60 Issue 6 Pages 2268-2270
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Stabilities of the oxocarbon dianions and some quasi-aromatic compounds can be rationalized in terms of Gimarc’s topological charge stabilization rule. The term “quasi-aromatic” is recommended for describing those non-aromatic compounds which behave like aromatics owing to the operation of this rule.
feedback
Top