Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 58 , Issue 2
Showing 1-50 articles out of 86 articles from the selected issue
  • Yoshitane Kojima, Tetsushi Yamashita, Shinya Nishide, Ken Hirotsu, Tai ...
    1985 Volume 58 Issue 2 Pages 409-413
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The crystal structure of cyclo(L-histidyl-L-histidyl) was determined by X-ray diffraction techniques, and was refined to a final R index of 0.066 for 680 reflections. This showed that one imidazolyl group of this compound faces the piperazine ring(folded) whereas the other is kept away from the ring(unfolded). A calculation using the α-β coupling-constant data of this peptide obtained by an 1H NMR measurement shows that the ratio of a folded conformation to an unfolded one is 49:51 in D2O. Also, NMR investigations of zinc(II) and silver(I) complexes with this peptide were carried out in D2O.
  • Tetsuya Osaka, Ichiro Koiwa, Yutaka Okabe, Hiroshi Matsubara, Akihide ...
    1985 Volume 58 Issue 2 Pages 414-419
    Published: 1985
    Released: June 27, 2006
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    A complete magnetic anisotropy film was formed by an electroless plating method for a high-density perpendicular recording medium. The Co alloy plating bath, using ammoniacal malonate–tartrate–succinate mixed complexing agents was studied mainly by varying three main metal ion factors in the bath: i.e., the concentrations of NiSO4, NH4ReO4, and MnSO4. The fine columnar structure of magnetic film in a cross section was confirmed by SEM observation. Three different kinds of eight-inch disks A, B, and C, were prepared under selected conditions with magnetic film thickness of 0.50, 0.25, and 0.20 μm respectively. The recording performance was evaluated with a Winchester ring head with a 0.33 μm gap length under various head-medium spacings. A perpendicular recording mode was confirmed, and the following recording densities were obtained: D50=54 and 58 kFRPI for disk A, and 57 and 63 kFRPI for disk B when using 0.20 and 0.15 μm practical usable spacing respectively, and D50=68 kFRPI for disk C when using the more advanced 0.12 μm spacing. It was suggested that the electroless cobalt alloy plating has a high potential as a process for producing perpendicular recording media.
  • Kazuhisa Hiratani
    1985 Volume 58 Issue 2 Pages 420-423
    Published: 1985
    Released: June 27, 2006
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    The electronic and fluorescence spectra of the alkali salts of noncyclic polyethers exhibiting selective transport for the lithium ion were investigated. In the electronic spectra hypochromicity in CH2Cl2 dependent on the kind of alkali metal ions was observed, and the magnitude of the hypochromic effect decreased in the following order: Li+>Na+>K+>Rb+>Cs+. Using the polar solvents, EtOH and MeCN, instead of nonpolar CH2Cl2, the hypochromicity is small. Also, in the fluorescence spectra, the quenching phenomenon dependent on the kind of alkali metal ions appeared in the same sequence as the hypochromicity in the electronic spectra. It is suggested that these results, together with our previous results, support a stacking structure between the terminal aromatic rings of the lithium salt in a nonpolar solvent, which has been proposed from the inspection of the CPK model building.
  • Kenji Kano, Tomonori Konse, Tanekazu Kubota
    1985 Volume 58 Issue 2 Pages 424-428
    Published: 1985
    Released: June 27, 2006
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    The effects of the pH and the temperature on the oxidation-reduction properties of the quinone moiety in adriamycin adsorbed on a mercury electrode surface have been investigated by means of cyclic d.c. voltammetry. The quinone waves have been fundamentally interpreted in terms of a two-step one-electron surface-redox reaction, even in a neutral or an alkaline solution, where the reduced product is liable to cause the following chemical reaction. The pH dependences of the standard surface-redox potential of the adsorbed adriamycin are −60 mV/pH (pH 2–6), −30 mV/pH (pH 7–8), and −60 mV/pH (pH 9–12). The semiquinone formation constant is 0.15 at pH 2–6 and 5 at pH 9–12. These results can be well explained by considering the protolytic equilibria of the phenolic hydroxyl groups among the oxidized, semiquinone, and reduced forms of adriamycin, the pKa’s of which are 8.53, 6.93, and 6.83 respectively. The thermodynamic constants of the semiquinone formation reaction at pH 4.5 have been determined to be ΔH=−24.6 kJ mol−1 and ΔS=−99.7 J K−1 mol−1.
  • Masako Tanaka, Susumu Sasaki, Meiseki Katayama
    1985 Volume 58 Issue 2 Pages 429-432
    Published: 1985
    Released: June 27, 2006
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    The near-infrared emission spectra were studied for xenon diluted with krypton, argon, and neon, respectively, in order to estimate the origin of an emission band at 1260 nm which was previously observed at several hundred Torr(1 Torr=133.2 Pa) of pure Xe irradiated with pulses of high-energy electrons. A continuous band around 1260 nm was observed only in Xe-Ar mixtures. This band appeared at Xe pressures above 20 Torr(diluted in 600 Torr of Ar) while it was detected above 190 Torr in pure Xe. In Xe–Ar mixtures, three emission lines due to Xe 5d(3/2)1 were also observed at 1700, 2020, and 2650 nm. On the basis of the reported kinetic data for the reactions of rare gas mixtures, the present results led to the conclusion that the band at 1260 nm was due to emission from highly excited excimer states, of which the dissociation limits were higher Rydberg states above the energy level of the Xe2+ ion.
  • Chikara Hongo, Masanori Tohyama, Ryuzo Yoshioka, Shigeki Yamada, Ichir ...
    1985 Volume 58 Issue 2 Pages 433-436
    Published: 1985
    Released: June 27, 2006
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    The asymmetric transformation of DL-p-hydroxyphenylglycine was achieved between two enantiomers by a combination of preferential crystallization of a desired enantiomer of p-hydroxyphenylglycine o-toluenesulfonate (HPG·o-TS) and the simultaneous racemization of the antipode. L-HPG·o-TS was easily racemized by heating at 100 °C in aqueous 95% (v/v) acetic acid in the presence of small amounts of salicylaldehyde and free DL-HPG. A supersaturated solution of DL-HPG·o-TS placed under such conditions for racemization was seeded with the crystals of D-HPG·o-TS, and added with DL-HPG and o-toluenesulfonic acid in order to provide continuously the supersaturated state of DL-HPG·o-TS as a driving force. As a result, 77.2% of DL-HPG added was transformed to D-isomer.
  • Atsuo Obata, Masahiro Yoshimori, Koh-ichi Yamada, Hiroshi Kawazura
    1985 Volume 58 Issue 2 Pages 437-441
    Published: 1985
    Released: June 27, 2006
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    The crystal structures of fenethazine hydrochloride hydrate (FTZ·HCl) and [FTZ H]2+·[CuCl4]2−(FTZ–Cu) were determined. FTZ·HCl crystallized in the monoclinic space group P21/a with a=8.686(1), b=31.660(2), c=6.140(1) Å, β=100.44(1)°, V=1660.5(3) Å3, and Z=4. FTZ–Cu crystallized in the triclinic space group P\bar1 with a=20.433(5), b=12.721(4), c=7.526(2) Å, α=91.31(3), β=94.56(3), γ=99.69(2)°, V=1920.9(1) Å3, and Z=4. The structures were solved using the heavy-atom method and were refined by the block-diagonal least-squares method. The final R values were determined to be 0.052 for FTZ·HCl and 0.050 for FTZ–Cu. The formation of a cation radical causes the phenothiazine ring of the FTZ molecule to be flattened; the dihedral angle between benzene rings is increased from 140.3° for FTZ·HCl to 174.7 or 167.5° for FTZ–Cu. The 2-aminoethyl chain holds a trans conformation in FTZ–Cu and a near gauche form in FTZ·HCl. In FTZ·HCl crystals, the FTZ molecules form a layer along a in which the molecules array the phenothiazine ring as faced with the ring in the neighboring layer. In FTZ–Cu, two FTZ molecules form a pair with a close overlap of the phenothiazine rings, directed approximately perpendicular to a. The CuCl42− is located so as to counterbalance both the positive charge of the ring and the protonated amino group of the side chain.
  • Shigeru Yamauchi, Yoichi Sakai, Takeshi Tominaga
    1985 Volume 58 Issue 2 Pages 442-446
    Published: 1985
    Released: June 27, 2006
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    The change of the Mössbauer line shape with the paramagnetic relaxation time was studied in several tris(β-diketonato)iron(III) complexes to determine the sign of the quadrupole splitting. The correlation observed between the molecular structure and the sign of the quadrupole splitting demonstrates that the sign should depend on the bond angle (∠O–Fe–O) in iron(III) complexes.
  • Shigeru Takagi, T. Ken Miyamoto, Yukiyoshi Sasaki
    1985 Volume 58 Issue 2 Pages 447-454
    Published: 1985
    Released: June 27, 2006
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    A new model compound “tulip garden” porphyrin, has a long half-lifetime, thus satisfying the demand for the synthetic analogue of myoglobin. At the same time, “tulip garden” porphyrin has high O2 affinities as compared to other protected porphyrins; especially, its Co(II) complex shows almost the same affinity (P1/2O2) as coboglobins. The difference in oxygen affinities between “tulip garden” and “picket fence-type” porphyrins can be ascribed to the bulkiness of pendant groups. The strong “side” influence of the adamantyl group can be expected to bring about a high O2 affinity.
  • Kosuke Izutsu, Toshio Nakamura, Katsumi Takizawa, Akihiko Takeda
    1985 Volume 58 Issue 2 Pages 455-458
    Published: 1985
    Released: June 27, 2006
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    A calorimetric method has been investigated for the determination of the thermodynamic parameters of acid dissociations in dipolar aprotic solvents. For the dissociations of monoprotonated bases BH+ (B: aniline, pyridine, triethylamine, tributylamine, triethanolamine, 1,3-diphenylguanidine and 1,1,3,3-tetramethylguanidine) in N,N-dimethylformamide, dimethyl sulfoxide (DMSO), acetonitrile and propylene carbonate, the solutions of the bases were titrated with small volumes of a “strong acid,” trifluoromethanesulfonic acid. In each solvent, there was an approximately linear relation of unit slope between ΔH298° and ΔG298° showing that the difference in pKa between different BH+’s can mainly be attributed to the difference in the enthalpy term. As for the solvent effect on pKa, however, the entropy term seems to play an important role. A preliminary study has shown that the calorimetric method is also applicable to the dissociations of HX-type weak acids (benzoic and salicylic acids in DMSO, for example), if the dissociation equilibria are not complicated by such reactions as homoconj ugation.
  • Taro Saito, Satoshi Sawada
    1985 Volume 58 Issue 2 Pages 459-463
    Published: 1985
    Released: June 27, 2006
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    The 1H NMR spectra of HMCo3(CO)12 (M=Fe or Ru) and HFeCo3(CO)12−x[P(OR)3]x (x=1–3, R=CH3; x=3, R=C2H5 or C6H5) showed very broad signals centered near δ=−21 at 27 °C. The band widths were generally smaller for the compounds of larger molecular volume, at lower temperatures and with higher viscosity of the solvent. These data were interpreted in terms of the quadrupole effects of 59Co nuclei to which the hydride proton was μ3-bonded. Supporting evidence was obtained from the 31P and 59Co NMR spectra and the relaxation time T1 of HFeCo3(CO)9[P(OCH3)3]3.
  • Norikazu Ueyama, Michio Nakata, Akira Nakamura
    1985 Volume 58 Issue 2 Pages 464-469
    Published: 1985
    Released: June 27, 2006
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    Tetrapeptides, Z–Cys–Ala–Ala–Cys–OMe(Z=benzyloxycarbonyl), Z–Cys–Val–Val–Cys–OMe, and Z–Cys–Gly–Pro–Cys–OMe, having Cys–X–Y–Cys sequences were synthesized by using an acetamidomethyl (Acm) protecting group. The Hg(II) complexes of these peptides, Hg2Cl2(Z–Cys–Ala–Ala–Cys–OMe) 1. Hg(Z–Cys–Ala–Ala–Cys–OMe) 2, Hg2Cl2(Z–Cys–Gly–Pro–Cys–OMe) 3, Hg(Z–Cys–Val–Val–Cys–OMe) 4, and Hg2Cl2(Z–Cys-Ala-Cys–OMe) 5 were synthesized by the reaction of the S(Acm) protecting peptides and HgCl2 in N,N-dimethylformamide. Two Raman bands due to Cl–Hg–S of 1, 3, or 5 were observed at 314, 281, or 276 cm−1 in solid, whereas a single band due to S–Hg–S was found at 326 cm−1 for 2 or 327 cm−1 for 4, in solid.
  • Jiro Yamamoto, Satoshi Ito, Takashi Tsuboi, Toshiaki Tsuboi, Kumiko Ts ...
    1985 Volume 58 Issue 2 Pages 470-472
    Published: 1985
    Released: June 27, 2006
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    From an equimolar mixture of DMSO and SbCl5 in carbon tetrachloride, a DMSO–SbCl5(1 : 1) complex (1) was formed as a white precipitate in a quantitative yield. The structure of 1 was determined by X-ray crystallographic analysis. Butyraldehydes, para-substituted benzaldehydes and benzils were obtained by the oxidation of butylalcohols, para-substituted benzylalcohols and benzoins using 1 as an oxidizing agent.
  • Michio Kobayashi, Masanori Kobayashi, Masato Yoshida
    1985 Volume 58 Issue 2 Pages 473-476
    Published: 1985
    Released: June 27, 2006
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    The triethylgermyl radical was found to react with thiosulfonic S-esters to generate sulfonyl radicals. The SH2 character of this new reaction was confirmed by a C-13 CIDNP study and products analysis. Selenosulfonic Se-ester reacts with germyl radical in a similar way.
  • Yuichiro Haramoto, Hiroyoshi Kamogawa
    1985 Volume 58 Issue 2 Pages 477-480
    Published: 1985
    Released: June 27, 2006
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    Trans and cis isomers of 2,5-disubstituted 1,3-dithianes were synthesized by the acid-catalyzed thioacetalization of p-substituted benzaldehydes and dithiols. The results of identifications of trans and cis isomers made by means of 13C-NMR chemical shifts indicate that the isomerism occurred at the 5 position in the 1,3-dithiane ring. Benzaldehydes with electrondonating p-substituents produced less cis isomers than that with the cyano group, which seems to indicate the establishment of an equilibrium in the formation reaction between trans and cis isomers. Several electro-optic properties of trans- and cis-2-(p-cyanophenyl)-5-alkyl-1,3-dithianes were determined by using them as a dopant of mixture of liquid crystals. Mixture added with trans isomers was superior to that added with cis isomers in several points.
  • Yasuhiro Fujioka
    1985 Volume 58 Issue 2 Pages 481-489
    Published: 1985
    Released: June 27, 2006
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    The absorption spectra of the charge-transfer (CT) complexes formed by two acceptors (tetracyanoethylene and 2,3-dichloro-5,6-dicyano-p-benzoquinone) with thirteen macrocyclic polyphenylenes and with thirty-eight linear polyphenyls were measured in dichloromethane. A linear relationship existing between the first transitions of the CT-complexes and those of the uncomplexed donor hydrocarbons made it possible to predict the CT-bands of new polyphenylenes and polyphenyls. By the gas-liquid chromatography using a glass capillary column, forty-nine polyphenyls and polyphenylenes, containing a large number of isomers, were successfully analyzed. The relationship between the retention times and the structure of linear polyphenyls was expressed by means of a simple empirical equation, and the equation was also applicable to the polyphenylenes by adding a correction factor. These equations are extremely useful for the estimation of the retention time and elution order and the structure of unknown polyphenyls and polyphenylenes. The reductive irradiation of m,m,o,p,o-pentaphenylene provided the bridged annulene compound. For six polyphenylenes and the related compounds, the criteria for the occurrence of the intramolecular photocoupling reaction were discussed. Among the examined polyphenylenes, m,o,o,m,o,o-hexaphenylene and o,p,p,o,p,p,o,p,p-nonaphenylene formed the adducts with several solvents.
  • Hisako Kobayashi, Masahiko Kato, Toshio Miwa
    1985 Volume 58 Issue 2 Pages 490-496
    Published: 1985
    Released: June 27, 2006
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    The titled compunds 1-exo-Cyano-1a,7b-dihydro-1H-cyclopropa[a]naphthalenes(8a), 1-endo-Cyano-1a,7b-dihydro-1H-cyclopropa[a]naphthalenes(8b), were photolyzed in several solvents. The results were: (1) The isomerization proceeded faster in aprotic nonpolar solvents than in polar ones. (2) The 1-endo derivative (8b) rearranged faster than the 1-exo-isomer (8a). (3) 8b was isomerized through Berson-Willcott rearrangement by the fission of bonds C1–C7b and C1–C1a, while 8a gave 1-cyanomethylnaphthalene (5b) as a main product. (4) Examination with an optically active 1-exo derivative (8a) showed that the exo-endo interconversion occured by the simultaneous two centered (30%) and one centered (70%) epimerization.
  • Yoshihiko Masuda, Masao Tanihara, Yukio Imanishi, Toshinobu Higashimur ...
    1985 Volume 58 Issue 2 Pages 497-504
    Published: 1985
    Released: June 27, 2006
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    The hydrolyses of a series of p-nitrophenyl carboxylates with different acyl chains were investigated at 25 °C, pH 7.8 using cyclic dipeptides[cyclo(–L- or D-Xyz–His–) consisting of L-histidine (L-His) and an α-amino acid (Xyz) with different aliphatic side chains] as catalysts. Consequently, cyclo(–D-Leu–L-His–) and cyclo(–D-Val–L-His–) were found to be specifically effective catalysts for the hydrolysis of p-nitrophenyl laurate. These trans (D-L-type) cyclic dipeptides were much more efficient catalysts than their diastereomers, and were more reactive than imidazole, despite the fact that the former are less basic than the latter. The conformation of the cyclic peptides in solution was investigated using proton magnetic resonance spectroscopy and the relationship between conformation and catalytic activity was investigated. Consequently, it was found that the hydrophobic interaction between a catalyst and a substrate and the stereochemical fit for the cooperation of functional groups in the intramolecular nucleophilic catalysis are very important in order to attain a highly efficient catalysis. It was also found that the functional groups should have a certain size and flexibility in order to realize an effective stereochemical fit between functional groups of catalysts and substrates.
  • Mutsuji Sakai, Toshiya Kimura, Toshiaki Nakaoka, Yasumasa Sakakibara, ...
    1985 Volume 58 Issue 2 Pages 505-507
    Published: 1985
    Released: June 27, 2006
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    Cyclohexadienes, 1,3-cyclohexadiene (1) and 1,4-cyclohexadiene (2), disproportionated to benzene (3) and cyclohexene (4) in the presence of catalytic amounts of metallic nickel prepared from nickel halides and zinc powder in N,N-dimethyformamide (DMF) under nitrogen.
  • Masaaki Honda, Kimiaki Imafuku
    1985 Volume 58 Issue 2 Pages 508-510
    Published: 1985
    Released: June 27, 2006
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    3-[3-(2-Furyl)-2-propenoyl]- (2a), 3-[3-(2-thienyl)-2-propenoyl]- (2b), 3-[3-(3-thienyl)-2-propenoyl]- (2c), and 3-[3-(3-pyridyl)-2-propenoyl]tropolone (2d) were prepared by the condensation of 3-acetyltropolone with the corresponding heterocyclic aldehydes. The compounds 2a–d were oxidized with selenium dioxide to afford 2-heterocycle-substituted cyclohepta[b]pyran-4,9-diones, while oxidation with both alkaline hydrogen peroxide and 2,3-dichloro-5,6-dicyano-p-benzoquinone gave 2-(heterocycle-substituted methylene)-2H-cyclohepta[b]furan-3,8-diones.
  • Yuji Takikawa, Kazuaki Shimada, Tetsuo Minami, Ryu Sato, Saburo Takiza ...
    1985 Volume 58 Issue 2 Pages 511-514
    Published: 1985
    Released: June 27, 2006
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    Reactions of substituted benzaldehydes with sodium hydrogensulfide in the presence of nitrobenzene, nitrosobenzene, or azobenzene in liquid ammonia produce the corresponding benzyl alcohols and benzamides. On the other hand, reaction of benzaldehyde with sodium sulfide produces benzyl alcohol and benzamide. A reaction mechanism has been proposed which involves benzaldehyde anion radical.
  • Tomoyuki Kusaba, Akira Mori, Hitoshi Takeshita
    1985 Volume 58 Issue 2 Pages 515-520
    Published: 1985
    Released: June 27, 2006
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    4,8-Dichloro- and 5,7-dichloro-2,10-dihydroxydicyclohepta[b,d]furan-3,9-diones were synthesized. Although the latter could be obtained by condensation of 4-chloro-p-tropoquinone and its hydroquinone, the former required the hydrolysis of condensate of 3-chloro-p-tropoquinone and 7-chloro-5-hydroxy-2-methoxytropone. This mixed condensation led to several unsymmetrically substituted derivatives in improved yields.
  • Masanobu Kojima, Hirochika Sakuragi, Katsumi Tokumaru
    1985 Volume 58 Issue 2 Pages 521-524
    Published: 1985
    Released: June 27, 2006
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    To investigate the photochemical electron transfer from aromatic olefins to copper(II) or iron(III) ions, a series of substituted styrenes (1) was irradiated in the presence of copper(II) or iron(III) salts in methanol, which gave dimethoxylated monomers (2) and one or more of three types of dimethoxylated dimers [α,α- (3), α,β- (4), and β,β,-dimers (5)]. The formation of these products are reasonably attributed to the participation of the cation radicals of the olefins generated by electron transfer from the excited olefins to the metal ions. Substituents on the substrates are found to govern the reaction products.
  • Yoshihisa Inoue, Mikio Ouchi, Tadao Hakushi
    1985 Volume 58 Issue 2 Pages 525-530
    Published: 1985
    Released: June 27, 2006
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    The solvent extraction of alkaline earth and heavy metal picrates with a series of ring-contracted and ring-enlarged crown ethers has been carried out in order to reveal the effects of methylene-chain length upon cation-binding ability. Compared with the parent 3m-crown-m, the ring-contracted crown ethers and their sila analogues possess limited extractabilities, often as low as those for the corresponding glymes. On the other hand, the ring-enlarged crown ethers, in general, show gradual, but not drastic, decreases in extractability for most cations with increasing methylene-chain length. Interestingly, the extractabilities for Ag+, Tl+, and Ba2+ do not decrease monotonously with ring expansion; in particular 16-crown-5 is a better extractant for Ag+ than 15-crown-5 and even than 18-crown-6. These results are accounted for in terms of cavity size, conformation, and molecular symmetry of crown ethers. Effects of cation hydration upon extractability and the limitations of solvent extraction technique are also discussed.
  • Makoto Tamaki, Tadashige Okitsu, Mie Araki, Honami Sakamoto, Michiaki ...
    1985 Volume 58 Issue 2 Pages 531-535
    Published: 1985
    Released: June 27, 2006
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    In order to investigate the contribution of configurations of amino acid residues around Pro residues in gramicidin S to its activity and conformation, [D-Val1,1′]- and [D-Val1,1′ L-Phe4,4′]-gramicidin S were synthesized by a liquid-phase method. The CD spectra of these analogs and gramicidin S in aqueous solutions differ from each other, indicating that these peptides have different conformations. These analogs have practically no activity against the Gram-positive microorganisms tested, indicating the importance of the presence of the D-Phe–Pro–Val sequence in gramicidin S regarding activity.
  • Tateaki Wakamiya, Yoshiaki Oda, Koichi Fukase, Tetsuo Shiba
    1985 Volume 58 Issue 2 Pages 536-539
    Published: 1985
    Released: June 27, 2006
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    Four stereoisomers of β-methyllanthionine were synthesized by coupling of N-enzyloxycarbonyl-3-methyl-D-cysteine with β-chloroalanine. 1H NMR analysis and retention time in amino acid analysis were studied on these compounds.
  • Noriyuki Mizoguchi
    1985 Volume 58 Issue 2 Pages 540-545
    Published: 1985
    Released: June 27, 2006
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    Within the London-McWeeny formalism of the π-electron magnetic properties, the contribution of each bond in a conjugated system to the London susceptibility is studied. By using the relations between the bond orders Prs and the imaginary bond-bond polarizabilities \barπ(rs)(tu) proved in a previous paper, it is shown that two equations, Prs+βπ(rs)(rs)=0 and π(rs)(vw)=0, hold for the “acyclic” bond r-s in a conjugated system. The equations show that no bonds in acyclic conjugated systems or in acyclic fragments of cyclic systems make any contributions to the London susceptibilities (or to the ring currents) of the systems. On the basis of these equations, the expression for the London susceptibility is simplified. Moreover, we will discuss the relationships between the above equations and some consequences of McWeeny’s unitary transformation.
  • Masayuki Nakagaki, Emiko Okamura
    1985 Volume 58 Issue 2 Pages 546-549
    Published: 1985
    Released: June 27, 2006
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    The interaction between the dimyristoyl phosphatidylcholine (DMPC) bilayers and aqueous copolymers of L-lysine and L-leucine was investigated by means of differential scanning calorimetry. None of the copolymers had any effects on the transition temperature of DMPC, irrespective of the lysine/leucine ratio, although the pretransition peak disappeared. The transition enthalpy did not appreciably change upon the addition of copolymers if the leucine fraction was small (<0.25), but it remarkably decreased upon the addition of a copolymer with a large leucine content (>0.3). The latter case suggests the penetration of copolymers into the hydrophobic region (hydrocarbon-chain region) of DMPC as a result of the hydrophobic effect of leucine residues. On the contrary, copolymers of a small leucine content can penetrate at most into the polar region of DMPC because of the electric charge derived from lysine residues, indicating the effect of the copolymer composition on the penetrability of a copolymer into lipid layers.
  • Gin-ya Adachi, Nobuhito Imanaka, Mineo Sato, Jiro Shiokawa
    1985 Volume 58 Issue 2 Pages 550-552
    Published: 1985
    Released: June 27, 2006
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    Calcium sulfides doped with tri- and tetravalent metal sulfides were prepared. Their electromotive forces (EMF) were measured on a galvanic cell(Fe+FeS| Solid Electrolyte| Cu+Cu2S) where the solid electrolyte was a material in a CaS–Ln2S3–MS2 system. The cell, using calcium sulfide doped with La2S3 and ZrS2, exhibited an EMF value as high as the one calculated for thermodynamical equilibrium. The CaS–La2S3–ZrS2 solid electrolyte showed, predominantly, an ionic conduction in the sulfur pressure range from 10−4 to 102 Pa with an activation energy of approximately 56.7 kJ·mol−1, which was lower than for CaS and CaS–La2S3.
  • Hirami Shimoishi, Shozo Tero-Kubota, Yusaku Ikegami
    1985 Volume 58 Issue 2 Pages 553-557
    Published: 1985
    Released: June 27, 2006
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    Solvent effects on the hyperfine splitting constants, monomer-dimer equilibrium, and kinetic parameters of the dimerization of the 1-methyl-2-methoxycarbonylpyridinyl radical have been examined in detail, using methylcyclohexane, toluene, 2-methyltetrahydrofuran, acetone, and acetonitrile as the solvents. A comparatively large activation energy for the fast step in the two-step dimerization mechanism suggests strongly that the dimeric intermediate is the 2,2′-dimer of the radical, which subsequently rearranges to the stable 4,4′-dimer.
  • Masayuki Aizawa
    1985 Volume 58 Issue 2 Pages 558-561
    Published: 1985
    Released: June 27, 2006
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    The spin-exchange rate of three kinds of hydrophobic nitroxide radicals with paramagnetic ions, Ni2+ ions, was measured in an aqueous sodium dodecyl sulfate (SDS) micellar solution at 30 °C. In the presence of SDS micelles, two of the three radicals had their spin-exchange rates accelerated, whereas the rate of the other radical was deaccelerated. These strange results were interpreted on the basis of a different solubilized location of the radicals in SDS micelles. The translational mobility of the Ni2+ ions on a micellar surface was estimated from the spin-exchange rate in the accelerated systems.
  • Hajime Katô, Yukiko Toyosaka, Tomonari Suzuki
    1985 Volume 58 Issue 2 Pages 562-568
    Published: 1985
    Released: June 27, 2006
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    When a mixture of 85Rb, 85Rb2, and D2 was irradiated by laser light at 5145 or 4880 Å, small visible particles appeared and the fluorescence spectra were observed. By analyzing these spectra, we determined the rotational constants Bv and the centrifugal distortion constants Dv and Hv for the X 1Σ+ and A 1Σ+ states of 85RbD. By considering the isotopic dependence of the Dunham coefficients, we determined various molecular constants of 85RbH whose values were in good agreement with the observed fluorescence spectra of 85RbH excited by laser lines at 4762, 4765, and 4880 Å. The process of RbH formation is discussed.
  • Tsuyoshi Kijima, Yoshiyuki Yajima
    1985 Volume 58 Issue 2 Pages 570-573
    Published: 1985
    Released: June 27, 2006
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    The hydrothermal reaction in the system ZrO2–P2O5–H2O in the presence of tetramethylammonium ions was examined within the temperature range 160–350 °C. This reaction resulted in the formation of framework zirconium phosphates (NH4)xH1−xZr2(PO4)3·yH2O (0.6≤x≤1,y≤0.3) as well as some other phases, including two tetramethylammonium intercalates. The framework phases were rhombohedral with lattice constants of, e.g., a=8.669 and c=24.23 Å for x=1.0. These phases were deammonated at 400–640 °C and converted to the proton-exchanged form HZr2(PO4)3. The protons of this phase are easily exchanged by unhydrated Li+ and Na+ ions, but not by K+ and Cs+, owing to the sieving effect of the bottleneck in the (Zr2P3O12)−1 framework. The acid strength of the proton form is a little weaker than that of α-zirconium phosphate.
  • Nobuhiko Sakai, Fumiko Sakai, Hisashi Sekizawa
    1985 Volume 58 Issue 2 Pages 574-579
    Published: 1985
    Released: June 27, 2006
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    The γ-ray radiolytic oxidation of Fe2+ ions in FexMg1−x(NH4)2(SO4)2·6H2O (x=1.0, 0.75, 0.56, 0.35, and 0.075) is studied by Mössbauer spectroscopy. For x≤0.75, a part of Fe2+ ions remain unoxidized even after heavy irradiation of 60Co γ-rays in contrast to the complete disappearance of Fe2+ ions for x=1.0. At least three kinds of Fe3+ ions are produced, and two of them order magnetically at liquid He temperature. Their saturated relative amount after heavy irradiation depends on the concentration of Fe, and is well explained by the random distribution probability of Fe and Mg ions among the six neighboring metallic sites around the Fe2+ ion.
  • Hayao Sakamoto
    1985 Volume 58 Issue 2 Pages 580-587
    Published: 1985
    Released: June 27, 2006
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    Mercury, arsenic, and antimony were determined in marine sediments collected from Kagoshima Bay, and their distribution was investigated. The contents of mercury, arsenic, and antimony in surface sediments were higher than those in the marine sediments of the open ocean. The average contents of mercury, arsenic, and antimony in surface sediments in the northern part of the bay were higher than in the southern part. The high-temperature sediments (about 200 °C) in the vicinity of a sea bottom fumarole, located at a depth of about 200 m in the northern part of the bay, showed abnormal concentrations of mercury, arsenic, and antimony derived from the fumarole gas; the contents of these components decreased sharply with an increase in the distance from the fumarole. A high degree of positive correlation was found among the contents of the three components (mercury, arsenic, and antimony) over the northern part of the bay. In contrast, no such correlation was observed in the southern part of the bay. This is in accord with the fact that volcanic activity is more vigorous in the northern than in the southern part of the bay.
  • Yasushi Inoue, Osamu Tochiyama
    1985 Volume 58 Issue 2 Pages 588-591
    Published: 1985
    Released: June 27, 2006
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    The complex formation of Np(V) in a carbonate medium has been studied in 1 mol dm−3 NaClO4 at pH 6.5–8.3 and 25 °C using the solvent-extraction method with thenoyltrifluoroacetone (TTA) and 1,10-phenanthroline. The formation constants of the complexes of Np(V) with CO32− were log(β1/mol−1 dm3)=4.14±0.01 and log(β2/mol−2dm6)=6.78±0.01, with no indication of the formation of HCO3 complexes. Based on these constants, the distribution of chemical species of neptunium are discussed under various conditions encountered in natural water.
  • Choichiro Shimasaki, Shigenobu Ookawa, Ryuichi Ishizaka
    1985 Volume 58 Issue 2 Pages 592-594
    Published: 1985
    Released: June 27, 2006
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    Das von einer Schwingungsmühle gemahlte Ammoniumhydrogenamidophosphat (NH4HPO3NH2) hat es herausgestellt, daß nach einer Stunde Laufzeit die erste endotherme Spitze in DSC Kurven in zwei Teile geteilt wird. Die Absorption infolge NH und Zwitterions in IR Spektren wird vom EinfuB der Schwingungsmühle verändert. Das Ergebnis unterstützt eine Transformation von NH4HPO3NH2 nach einer Zwischenphase, die durch die starke Wasserstoffbindung zwischen NH und POH gebildet worden hat.
  • Yuichi Fujimura, Yukiyoshi Ohtsuki, Takeshi Nakajima
    1985 Volume 58 Issue 2 Pages 595-600
    Published: 1985
    Released: June 27, 2006
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    A theory of time-resolved resonance Raman scattering (RRS) from molecules is developed. The time-resolved RRS cross section is defined as a product of the time-dependent vibronic energy distribution and the scattering cross section from the single vibronic level. The theory is applied to the time-resolved RRS from vibrationally hot molecules whose vibronic distribution characterized by a canonical distribution with temperature higher than that of the heat bath relaxes to the equilibrium one in the presence of a collisional vibrational relaxation. Analytical expressions for the time-resolved RRS cross section are derived within a displaced harmonic oscillator model. It is shown that in the strong coupling case the intensities of the Stokes and anti-Stokes Raman bands in the rigorous resonance case vary inversely as the time-dependent average vibrational occupation number. Some model calculations are performed to illustrate the time-dependent intensity changes of the Raman bands.
  • Satoshi Inagaki, Koji Iwase, Hirofumi Kawata
    1985 Volume 58 Issue 2 Pages 601-610
    Published: 1985
    Released: June 27, 2006
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    Acyclic localization-delocalization of electrons in π-conjugated hydrocarbon polyions was predicted in terms of the continuity-discontinuity of the phase of the component orbitals. Many pairs of electron-localizing and -delocalizing conjugated polyions were designed as the model systems of which the relative stabilities have not been explored so far.
  • Isao Kojima, Eizo Miyazaki, Yasunobu Inoue, Iwao Yasumori
    1985 Volume 58 Issue 2 Pages 611-617
    Published: 1985
    Released: June 27, 2006
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    WC, W2C, and W were comparatively studied for CO hydrogenation to reveal the catalytic role of carbon alloyed with metals. The main products of the reaction were CH4, CO2, and H2O on these catalysts, but the kinetic data obtained for WC catalyst were different from those for W2C and W catalysts: i.e., the apparent activation energies for CO consumption and for CH4 formation on WC were found to be about three times larger than those on W2C or W. Furthermore, the catalytic activity of WC was about 20 times larger than that of W2C and W. It was suggested that the hydrogenation of CO on WC proceeds via direct hydrogenation of adsorbed CO forming a CHO adsorbed species as an intermediate, whereas on W2C and W catalysts, dissociation of CO occurs in the initial step, followed by further hydrogenation of adsorbed carbon to form CH4. X-ray photoelectron spectroscopic (XPS) studies on WC and W2C showed that the WC surface catalytically activated was almost free from graphite carbon and oxygen as poison, but W2C surface was largely covered with graphite carbon. These distinctive catalytic behavior differences between the carbide catalysts are discussed on the basis of the structure of the active surfaces.
  • Hiroshi Maeda
    1985 Volume 58 Issue 2 Pages 618-22
    Published: 1985
    Released: June 27, 2006
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    The stability of uncharged β-structure of polypeptides from potentiometric titrations is examined based on thermodynamic considerations with special references to the aggregation and/or precipitation of polypeptides and the irreversible nature of the titration. It is concluded that most of the reported data on various kinds of polypeptides approximately represent the stability of the β-structure. Diverse stabilities exhibited by reported data can be partly ascribed to different extents of the stacking of the pleated sheets.
  • Kohji Ichimori, Hiroaki Ohya-Nishiguchi, Noboru Hirota, Kiyoko Yamamot ...
    1985 Volume 58 Issue 2 Pages 623
    Published: 1985
    Released: June 27, 2006
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    The ESR spectra of the π-cation radical generated electrochemically from 5,10,15,20-tetraphenylporphyr-inatocobalt(II), [CoII(tpp)], have been observed in the presence of various anions and in solvents such as halo-genated hydrocarbons, nitriles, ethers, ethanol, and organic acids. From the analyses of these spectra, the TT-cation radical has been found to coordinate axially the anion or the solvent according to the order of its coordinating ability; BF4, ClO4, PF6, NO3<nitriles<halogen anions<ethanol<CF3COO, AcO, SCN, CN. The singly-occupied molecular orbital has been assigned to be always a2uπ orbital regardless of the axial ligands. The spin densities on N and Co much increase due to the axial ligation. It has been further confirmed that the spin polarization mechanism mainly contributes to the appearance of the spin density on Co. These axial-ligand effects are quantitatively explained by a model calculation of the CNDO/2 MO method.
  • Yôichi Iida
    1985 Volume 58 Issue 2 Pages 631-633
    Published: 1985
    Released: June 27, 2006
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    DNA sequences of calmodulin genes taken from chicken and electric eel were examined to investigate the molecular evolution of its protein. One notable feature of the amino acid coding region of the gene is that it can be subdivided into four domains having a similar amino acid sequence. In the present paper, an intramolecular evolutionary tree was constructed with the DNA sequences of the four domains.
  • Takayuki Ohmae
    1985 Volume 58 Issue 2 Pages 634-637
    Published: 1985
    Released: June 27, 2006
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    The propagator method is applied to the study of solvent effects on reactivities of aromatic substitution reactions. We obtain the following set of results: (1) The influence of nonpolar solvent on electrophilic reactions is opposite to that on nucleophilic reactions; (2) the solvent which has the large dielectric constant weakens the directive power of a substituent group; (3) frontier orbitals control solvent effects on the chemical reactivities of aromatic substitution reactions.
  • Yoshifumi Nishimura, Masamichi Tsuboi, Shigeki Kato, Keiji Morokuma
    1985 Volume 58 Issue 2 Pages 638-645
    Published: 1985
    Released: June 27, 2006
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    Harmonic force constants, in-plane vibrational frequencies, and in-plane vibrational modes of guanine have been calculated by an ab initio MO method. The force constants were calculated by the use of an energy gradient method with STO-3G basis set, and then they were corrected into “4-31G force constants” by the scaling factors given by us previously for the case of uracil. The corrected set of force constants could reproduce the observed frequencies of guanine, guanine-7, 9-15N2, guanine-1,3,amino-15N3 (at positions 1, 3 and amino), guanine-8-d (at position 8), guanine-1,9, amino-d4 (at amino and iminos), and guanine-d5. The calculated vibrational modes could also account for the results of earlier experiments on infrared and Raman spectra of guanine residues in 5′-GMP and other nucleotides.
  • Y\={u}ko Aimoto, Wakako Kanda, Sadatoshi Meguro, Y\={u}ji Miyahara, Hi ...
    1985 Volume 58 Issue 2 Pages 646-650
    Published: 1985
    Released: June 27, 2006
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    Catalytic oxygenation of t-butylphenols has been examined with the cobalt(III) complexes with N,N′-disalicylideneethylenediamine (H2salen), K[Co(salen)CO3], Na[Co(salen)(N3)2], K[Co(salen)(CN)2], [Co(salen)(py)2]PF6, and [Co(salen)(NH3)2]PF6. The CO3-complex showed a high catalytic activity while the other complexes a low or no catalytic activity. Based on electronic and ESR spectral investigations, it has been shown that the reaction is initiated by the direct oxidation of t-butylphenols by the CO3-complex through a phenolatocobalt(III) intermediate.
  • Kazuko Matsumoto
    1985 Volume 58 Issue 2 Pages 651-656
    Published: 1985
    Released: June 27, 2006
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    Nonstoichiometric platinum tetranuclear compound, cis-Diammineplatinum α-Pyrrolidone Violet, [Pt4(NH3)8(C4H6NO)4)(PF6)2(NO3)2.56·5H2O, has been synthesized and the crystal structure has been solved with X-ray diffraction analysis. The crystal is triclinic with the space group of P\bar1 and cell dimensions of a=13.530(8), b=19.242(9), c=10.222(3) Å, α=96.56(9), β=93.82(9), γ=74.64(8)°, V=2547.4 Å3, and Z=2. The structure have been solved by heavy atom method and the final discrepancy index R1 was 0.094 and R2 was 0.090. The cation is structurally identical with those of cis-Diammineplatinum α-Pyridone Yellow(PPY), [Pt4(NH3)8(C5H4NO)4]4+, cis-Diammineplatinum α-Pyridone Blue(PPB), [Pt4(NH3)8((C5H4NO)4]5+, and cis-Diammineplatinum α-Pyrrolidone Tan(PPT), [Pt4(NH3)8(C4H6NO)4]6+, and consists of four platinum atoms linked in a chain with bridging pyrrolidone ligands. Each platinum atom is cis coordinated by two ammine ligands and either two exocyclic oxygen atoms or two deprotonated ring nitrogen atoms of α-pyrrolidone ligands. The Pt-Pt bond distances are 2.848(2), 2.875(2), 2.839(2), and 2.875(2) Å, which are intermediate between those of PPY and PPB, indicating that the average platinum oxidation state is between 2.0 and 2.25. According to the potentiometric: oxidative titration of the compound using Ce(IV), the average platinum oxidation state is 2.14 and therefore the compound is considered to consist of 44% of [Pt4(NH3)8(C4H6NO)4]4+ and 56% of [Pt4(NH3)8(C4H6NO)4]5+.
  • Fumiyo Sasakura, Kiyoshi Isobe, Shinichi Kawaguchi
    1985 Volume 58 Issue 2 Pages 657-663
    Published: 1985
    Released: June 27, 2006
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    cis- and trans-[PtCl2(Et2S)2] as well as [PtCl2(EtSCH2CH2SEt)] reacted with thallium(I) β-diketonates, Tl(β-dik), to give complexes containing a central-carbon-bonded β-dik ligand. The reaction of cis-[PtCl2(PEt3)2] with Tl(acac) (acac=acetylacetonato) did not give an acetylacetonato complex, but resulted in [Pt(CO3)(PEt3)2], while trans-[PtCl2(PEt3)2] yielded [PtCl(acac)(PEt3)]. [Pt(PPh3)2(H2O)2](ClO4)2 derived from cis-[PtCl2(PPh3)2] reacted with K(acac) and K(tfac) (tfac=trifluoroacetylacetonato) to afford [Pt(acac)(PPh3)2]ClO4 and [Pt(tfac)(PPh3)2]ClO4, respectively. Bases such as Et3N, K(acac), and K(tfac) removed a proton from the latter complex to give [Pt(tfac(2–)-C,O)(PPh3)2] containing a C,O-chelated tfac dianion.
  • Hideyuki Sugimura, Hisashi Takei
    1985 Volume 58 Issue 2 Pages 664-666
    Published: 1985
    Released: June 27, 2006
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    6-(Methylthio)purine reacted with RMgX (R=C6H5, CH3(CH2)nCH2 (n=2 to 6), C6H5CH2CH2, (CH3)2 C=CHCH2CH2) in the presence of 5 mol% [NiCl2(Ph2PCH2CH2CH2PPh2)] in refluxing THF for 8 h to afford 6-aryl or 6-alkylpurines in 62–74% yields. By applying this reaction to 6-(methylthio)purine nucleoside, 6-(4-methyl-3-pentenyl)-9-β-D-ribofuranosylpurine was synthesized.
  • Hideyuki Tanaka, Shunichi Kametani, Takao Saito, Shinichi Motoki
    1985 Volume 58 Issue 2 Pages 667-674
    Published: 1985
    Released: June 27, 2006
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    2,9-Dithia-1-phosphabicyclo[4.3.0]nona-3,7-diene 1-sulfides have been prepared by the reaction of α,β unsaturated ketones with P4S10 in the presence of NEt3. 1,2-Thiaphosphole 2-sulfides generated by the thermolysis of the phosphabicyclo compounds underwent cycloaddition reactions with acrylonitrile, styrene, butyl vinyl ether and norbornene to give the [4+2]cycloadducts, respectively.
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