Chemical and Pharmaceutical Bulletin
Online ISSN : 1347-5223
Print ISSN : 0009-2363
ISSN-L : 0009-2363
Volume 15, Issue 10
Displaying 1-25 of 25 articles from this issue
  • Nobuyoshi Kaneniwa, Akiko Ikekawa, Haruko Aoki
    1967 Volume 15 Issue 10 Pages 1441-1445
    Published: October 25, 1967
    Released on J-STAGE: March 31, 2008
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    Angles of repose and sliding angles of sodium borate and boric acid powders are investigated by four methods. These angles gradually increase with decrease of particle size by any method, and critical diameters are found to be 160μ for sodium borate and 110μ for boric acid powders. The relation between angle (α) and particle diameter (D) is represented as follows. D≤Dc tan α=A1 exp (-B1D) D≥Dc tan α=A1'exp (-B1'D) A1>A1' B1>B1'>0 It is concluded that the cohesive force between particles of powders is negligibly small in the region of particle diameter larger than the critical size, and the cohesive force remarkably influences the angle at smaller diameters. The following relation is found between C/Mg and D, in the case of sodium borate powders. C/Mg=0.81 exp (-147 D)
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  • Akira Hanaki, Tohru Hino, Sanya Akaboshi
    1967 Volume 15 Issue 10 Pages 1446-1452
    Published: October 25, 1967
    Released on J-STAGE: March 31, 2008
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    The conjugate bases of AET and APT are transguanylated rapidly and nearly quantitatively to MEG and MPG respectively, which are determined spectrophotometrically with ferric 1, 10-phenanthrolinate. The ferric complex enhanced the transguanylation of AET, but not APT. This finding suggests the possibility that AET would be easily transguanylated by metal ions or metal complexes which is contained in the body fluid, even though AET itself is injected. Aminothiols, such as MEA, MEG and MPG, displayed two maxima of the reduction abilities ; one appeared at pH 3.2 and another at pH 5.0, and a minimum at pH 4.0. At those two pH regions, the reaction pathways and the products might be different. As the acidic region, the reductivities were parallell with the acidities of the aminothiols.
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  • Osamu Yamauchi, Hisashi Tanaka, Toyozo Uno
    1967 Volume 15 Issue 10 Pages 1453-1460
    Published: October 25, 1967
    Released on J-STAGE: March 31, 2008
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    The Schiff bases from 4 (5)-imidazolecarboxaldehyde and aromatic amines (type [A]), those from 4 (5)-amino-5 (4)-methylimidazole and aromatic aldehydes (type [B]), and 4 (5)-aminomethylimidazoles (type [C]) were prepared. The compounds [A] and [C] react with Fe (III), Cu (II), Pd (II), Pt (IV), Au (III), ect. to give green∼brown colors, whereas the compounds [B] give only faint colors with Cu (II), Pt (IV), and Au (III). The copper chelates of type Cu (ligand)2Br2, where the ligands are the compounds [A] and [C], were isolated, and the binding site of the imidazole nucleus was determined to be the pyridine nitrogen by comparing the IR spectra with those of the deuteration products and of the copper chelate of type Cu (ligand)2. The reactivities of the compounds [A] and [C] suggest that they behave as bidentate ligands.
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  • Mitsuo Watanabe, Morizo Ishidate
    1967 Volume 15 Issue 10 Pages 1461-1469
    Published: October 25, 1967
    Released on J-STAGE: March 31, 2008
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    1. An available method of determination of biliary and urinary metabolites of DAB in rat was devised. 2. Twelve metabolites of DAB (DAB, MAB, AB, 4'-OG-DAB, 4'-OG-MAB, 4'-OG-AB, 4'-OG-AB-NAc, 4'-OS-DAB, 4'-OS-MAB, 4'-OS-AB and 4'-OS-AB-NAc in bile, and PAP-OS in urine) in rats administered with DAB were determined.
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  • Akira Minato, Hisashi Fukuzawa, Seiyu Hirose, Yasuko Matsunaga
    1967 Volume 15 Issue 10 Pages 1470-1477
    Published: October 25, 1967
    Released on J-STAGE: March 31, 2008
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    The percutaneous absorbability of water-soluble substances from emulsion-type ointments was demonstrated by measuring the absorption of radioactivity after application of hydrophilic and absorption ointments containing Na131I, 59Fe-EDTA, 59Fe-tiron or 22NaCl to hairclipped mouse skin. The absorption of lipid-soluble 59Fe-cupferron and 59Fe-carbamate from these vehicles was quite small. The large promoting effect of polyethylene oleyl ether on the percutaneous absorption of 59Fe-EDTA from polyethylene glycol 1500 through mouse skin suggested some important contribution of surface-active agents to the percutaneous absorption of water-soluble substances from hydrophilic and absorption ointments.
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  • Susumu Ishiguro, Setsuzo Tejima
    1967 Volume 15 Issue 10 Pages 1478-1484
    Published: October 25, 1967
    Released on J-STAGE: March 31, 2008
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    2-O-Mesyl-3, 4, 6-tri-O-acetyl-β-D-glucopyranosyl N, N-dialkyldithiocarbamate (VI or VII, VI : methyl, VII : ethyl) was prepared starting from the corresponding bromide by treatment with sodium N, N-dialkyldithiocarbamate (III or IV, III : methyl, IV : ethyl). Reflux of a mixture of VI or VII and potassium thiolacetate in acetone-ethanol afforded 2-S-acetyl-2-thio-3, 4, 6-tri-O-acetyl-β-D-mannopyranosyl N, N-dialkyldithiocarbamate (VIII or IX, VIII : methyl, IX : ethyl) in 30 to 40% yield. The structure was confirmed by UV, IR, NMR and the formation of 3, 4, 6-tri-O-acetyl-D-hydroglucal. When a mixture of VI and potassium acetate in acetone-ethanol was refluxed for one hour, crystals (XI), m.p. 104°, [α]20D+185.8° were obtained in 93% yield. The product was also obtainable by acetylation of 1, 2-dideoxy-1, 2-(N, N-dimethylammonium)-dithiocarbonyl-β-D-mannopyranose methanesulfonate (XIII) which was prerared starting from VI, by deacetylation and successive evaporation of an aqueous solution of the deacetylated product. The structure of XI was assigned to be 2-N, N-dimethyldithiocarbamoyl-2-deoxy-3, 4, 6-tri-O-acetyl-D-arabino-hexopyranose-1-ene, and the reaction mechanism of the formation was discussed. Deacetylation of XI afforded 2-N, N-dimethyldithiocarbamoyl-2-deoxy-D-arabino-hexopyranose-1-ene (XIV), m.p. 157°, [α]20D+131.9° which is a new type of unsaturated sugars. The nuclear magnetic resonance spectroscopy helped greatly in the determination of the structures of compounds in this series.
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  • Isamu Utsumi, Toshio Watanabe, Kiyoshi Harada, Goro Tsukamoto
    1967 Volume 15 Issue 10 Pages 1485-1492
    Published: October 25, 1967
    Released on J-STAGE: March 31, 2008
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    Refluxing of monosulfoxide (Ia) of O-benzoylthiamine disulfide in aqueous ethanol or an alkaline decomposition of the compound Ia provided a new compound, O-benzoylhypothiaminic acid (II) which is presumed to be an intermediate in the course of formation of O-benzoylthiaminic acid (VI). An alkaline hydrolysis of II afforded hypothiaminic acid (V). These hypothiaminic acids were oxidized to the corresponding thiaminic acids by hydrogen peroxide. From the fact that, in refluxing the compound Ia in aqueous ethanol, O-benzoylthiamine disulfide (III) was formed besides the compound II, it seemed reasonable to assume that the decomposition pathway is disproportionation and the alkaline decomposition is similar hydrolysis to that of carboxylic esters to give the sulfinic acid (II) and thiol (IV).
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  • Satoshi Kawai, Zenzo Tamura
    1967 Volume 15 Issue 10 Pages 1493-1497
    Published: October 25, 1967
    Released on J-STAGE: March 31, 2008
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    Separation of catecholamines by gas chromatographic technique requires the preparation of suitable derivatives. A procedure has been developed which involved the treatment of amine mixtures with hexamethyldisilazane in dimethyl sulfoxide followed by the addition of an aliphatic ketone. Hydroxyl groups are converted into trimethylsilyl ether and primary amines are converted into Schiff bases. Secondary amino group remains unchanged. The separations were carried out with a 7% DC 1107 column. Catecholamines extracted from bovine adrenal medulla were separated and estimated under these conditions and good reproducible data were obtained.
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  • Takao Sekiya, Tyunosin Ukita
    1967 Volume 15 Issue 10 Pages 1498-1502
    Published: October 25, 1967
    Released on J-STAGE: March 31, 2008
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    The reactions of 2, 2'-anhydrouridine (I) with hydrogen sulfide (Reaction A) and of I, 3', 5'-di-O-benzoyl-2, 2'-anhydrouridine (III) and 1-(3', 5'-di-O-benzoyl-2'-methanesulfonyl-β-D-arabinofuranosyl) uracil (V) with thiobenzoate or xanthogenate nucleophiles (Reactions B), were investigated with the purpose of introducing thiol substituents at the 2'-position. The Reaction A afforded 1-β-D-arabinofuranosyl-2-thiouracil (II) as only sulfur containing product and the Reactions B gave no sulfur containing product but resulted in a partial liberation of uracil.
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  • Takao Sekiya, Tyunosin Ukita
    1967 Volume 15 Issue 10 Pages 1503-1507
    Published: October 25, 1967
    Released on J-STAGE: March 31, 2008
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    A complex neighboring approach provided a successful synthesis of 2'-deoxy-2'-thio-3'-deoxy-3'-aminouridine (IX). 1-(3'-Deoxy-3'-amino-β-D-arabinofuranosyl) uracil (I) afforded, in three steps, the blocked dithiocarbamoyl mesylate (IV), which, on heating in pyridine, cyclized to the thiazoline (V), that was deblocked to VI and reduced to the thiazolidine (VII). Compound (VII) was successively treated with mercuric chloride and hydrogen sulfide to furnish the desired product (IX).
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  • Kenji Suzuki, Takashi Abiko
    1967 Volume 15 Issue 10 Pages 1508-1513
    Published: October 25, 1967
    Released on J-STAGE: March 31, 2008
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    The synthesis of the analogs of bradykinin listed in the title are described in which glycine residue in 4-position of bradykinin, 6-L-threonine-bradykinin, and their 6-O-acetyl compound is substituted for another amino acid residues having bulky side chain. The biological activity of the ten analogs is compared with that of bradykinin on an isolated guinea pig ileum.
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  • Hiroshi Enomoto, Takeshi Yamaguchi
    1967 Volume 15 Issue 10 Pages 1514-1520
    Published: October 25, 1967
    Released on J-STAGE: March 31, 2008
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    1. A study was made of 42 substances, including catalase, metal chelating agents and peroxidase substrates as to their effects on the over-all course of aerobic reduction of cytochrome c by xanthine oxidase. 2. It was found that 8-hydroxyquinoline and m-phenylenediamine completely prevented the reoxidation of reduced cytochrome c in concentrations above 3.3×10-5 and 1.7×10-5 M, respectively. A similar, but less marked, effect was obtained with small amounts of catalase and KCN. 3. This enabled the determination of enzymically reducible cytochrome c except polymeric or CO-sensitive cytochrome c included in the preparation, by xanthine oxidase, with the use of 8-hydroxyquinoline and m-phenylenediamine. 4. 8-Hydroxyquinoline and m-phenylenediamine had an inhibitory effect on the peroxidase activity of cytochrome c.
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  • Hiroshi Enomoto
    1967 Volume 15 Issue 10 Pages 1521-1528
    Published: October 25, 1967
    Released on J-STAGE: March 31, 2008
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    1. In the presence of 8-hydroxyquinoline the reduction of cytochrome c by xanthine oxidase was markedly accelerated by H2O2 under both aerobic and anaerobic conditions. 2. The accelerating effect of H2O2 was induced only when H2O2 was preincubated with 8-hydroxyquinoline and cytochrome c, and this effect was dependent on the concentration of each component and on the period of preincubation time. 3. Thin-layer chromatography showed that 5, 8-dihydroxyquinoline and 5, 8-quinolinedione were present both in aerobically incubated medium containing hypoxanthine, xanthine oxidase, cytochrome c and 8-hydroxyquinoline and in aerobically or anaerobically incubated medium containing cytochrome c, 8-hydroxyquinoline and H2O2. These two quinoline derivatives were proved to be potent electron carriers between xanthine oxidase and cytochrome c. 4. As a plausible explanation for the mechanism of action of 8-hydroxyquinoline in inhibiting the reoxidation and in accelerating the reduction of cytochrome c, it was proposed that 8-hydroxyquinoline is hydroxylated to 5, 8-dihydroxyquinoline by the peroxidative action of cytochrome c, and this reaction product acts as an electron carrier which promotes the anaerobic type of reduction of cytochrome c.
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  • Satoshi Omura, Michiko Katagiri, Haruo Ogura, Toju Hata
    1967 Volume 15 Issue 10 Pages 1529-1533
    Published: October 25, 1967
    Released on J-STAGE: March 31, 2008
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    Leucomycin A3 is a new antibiotic which has been isolated along leucomycin A1 and other components, from the fermentation broth of Streptomyces Kitasatoensis HATA. The present paper is concerned with the partial structure of leucomycin A3 as a macrolide antibiotic and composed of a lactone containing aldehyde, O-acetyl and O-methyl groups, mycaminose, and 4-O-isovaleryl mycarose.
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  • Kiichiro Kakemi, Takaichi Arita, Ryohei Hori, Ryoji Konishi
    1967 Volume 15 Issue 10 Pages 1534-1539
    Published: October 25, 1967
    Released on J-STAGE: March 31, 2008
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    The absorption of the unionized forms of barbituric acid derivatives from rat stomach was found to be a first order process and varied with the differences in the chemical structures. N-methylation and O-S displacement markedly affected the gastric absorption. The mediated physicochemical factor was partition coefficient to organic solvent. Effect of pH of drug solution also influenced the absorption of especially readily absorbed derivatives. In respect to ionized forms, the similarity in rate constants was observed among all series of derivatives, and the mechanism involved was assumed to be a physical diffusion through pores. From these observations, it was concluded that all types of barbituric acid derivatives are absorbed from rat stomach by a relatively simple physical process, which is in good agreement with pH-partition process suggested by Brodie, et al.
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  • Shigeharu Inouye
    1967 Volume 15 Issue 10 Pages 1540-1556
    Published: October 25, 1967
    Released on J-STAGE: March 31, 2008
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    The structures and solution equilibria of twenty members of N-salicylidene-amino-sugars and -amino-alcohols were examined mainly in methanol, water and solid state. As the modeled compounds were examined simultaneously three members of N-salicylidene-alkylamines and eight members belonged to the o-methoxybenzylidene, 3-methoxysalicylidene, 3, 5-dibromosalicylidene and 2-hydroxynaphthylidene derivatives. From the comparative studies on the electronic, infrared, NMR spectra and equilibrium position, it was shown that the solution equilibrium consisted of the phenolimine and the ketoamine species, the latter being stabilized by the intra- and intermolecular hydrogen bonding involving the alcoholic hydroxyl groups and protic solvents. The acid-base equilibria of the two tautomers in methanol and the ketoamine-ion-pair equilibrium in water were discussed.
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  • Shigeharu Inouye
    1967 Volume 15 Issue 10 Pages 1557-1566
    Published: October 25, 1967
    Released on J-STAGE: March 31, 2008
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    Optical rotatory dispersion and circular dichroism curves of sixteen members of N-salicylideneamino-sugars were meaured in methanol and, in part, in dioxane. It was found for the D-glucose derivatives that the positive Cotton effects near 405, 315 and 255 mμ were correlated with the D (S) configuration of the C-2 chromophore and that the negative sign with the L (R) configuration of the C-1 and C-3 chromophores. The Schiff bases showing strong absorption at 405mμ exhibited strong Cotton effect near 405mμ, which was qualitatively interpreted in terms of the intramolecular hydrogen bonding asymmetric solvation to the optically active azomethine. The optical rotatory dispersion curves of poly-N-salicylidene derivatives were determined not only by the rotatory power of the individual chromophores but by relative amounts of tautomers equilibrated in solution.
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  • Manki Komatsu, Tsuyoshi Tomimori, Yukiko Makiguchi
    1967 Volume 15 Issue 10 Pages 1567-1572
    Published: October 25, 1967
    Released on J-STAGE: March 31, 2008
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    1. Swertiajaponin, C22H22O11, m.p. 265° (decomp.), was newly isolated from the whole herb of Swertia japonica MAKINO (Gentianaceae), and identified as 6-C-β-D-glucopyranosylluteolin-7-methylether. 2. Iso-swertiajaponin, C22H22O11, m.p. 258∼261° (decomp.) was obtained by the acidtreatment of swertiajaponin, and formulated as 8-C-β-D-glucopyranosylluteolin-7-methylether. 3. At the same time, it was found that they were interconvertible into each other by boiling with mineral acids, reminiscent of the interrelationship between swertisin and isoswertisin.
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  • Yukio Kameda, Katsuhiko Matsui
    1967 Volume 15 Issue 10 Pages 1573-1577
    Published: October 25, 1967
    Released on J-STAGE: March 31, 2008
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    Screening experiments for δ-ornithine acylase activity in soil bacteria have been carried out for the purpose of finding out new enzymes. A number of bacteria were cultured on the medium containing 5-N-acyl-L-ornithine, and the cultural broth were examined the liberated ornithine by paper chromatography. Then, δ-ornithine acylase activities of these bacteria, which appeared a distinct spot of ornithine, were measured by estimation of liberated ornithine after incubation of 5-N-acyl-L-orthinine with their acetone powder. As a result, the δ-ornithine acylase activity was observed in some soil bacteria and a strain (KT 801) showed the highest activity. KT 801 was isolated by using the synthetic medium containing 5-N-benzoyl-L-ornithine as a sole source of carbon and confirmed to belong in Pseudomonas group. δ-Ornithine acylase of KT 801 hydrolyzes 6-N-acyl-L-lysine and 5-N-acyl-L-ornithine, although KT 83 (Pseudomonas sp.) hydrolyzes 6-N-acyl-L-lysine but not 5-N-acyl-L-ornithine, and KT 511 (Brevibacterivm sp.) hydrolyzes ω-phenylacetyl derivatives of lysine and ornithine but not the benzoyl derivatives.
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  • Katsuhiko Matsui, Michihiko Kumagai, Yukio Kameda
    1967 Volume 15 Issue 10 Pages 1578-1585
    Published: October 25, 1967
    Released on J-STAGE: March 31, 2008
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    Since KT 801 (Pseudomonas sp.) isolated from soil showed mardedly high δ-ornithine acylase (5-N-acylornithine amidohydrolase) activity, purification of the enzyme have been attempated. In the first place, cultural conditions for the production of this enzyme were investigated. As a result, it was confirmed that a medium containing 0.1% 5-N-benzoyl-L-ornithine, 1% peptone and some inorganic salts is most suitable for the enzyme production and that more δ-ornithine acylase is produced by shaken culture or submerged culture in jar fermentor than by stationary culture. Then, δ-ornithine acylase was extracted by means of freezing and thawing method from KT 801 cells. By this method, 60∼70% of the enzyme activity estimated in cell suspension was extracted, although only 5∼8% of cellular proteins was extracted. Subsequently, δ-ornithine acylase was purified by fractionation with ammonium sulfate and chromatography on DEAE cellulose and DEAE Sephadex A-50. The specific activity of the purified enzyme preparation was 41, 280 μM/hr./mg. and it was represented abut 300 fold purification over the original cell suspention. This enzyme preparation gave single peak in Tiselius electrophoresis or analytical ultracentrifuge.
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  • Katsuhiko Matsui
    1967 Volume 15 Issue 10 Pages 1586-1596
    Published: October 25, 1967
    Released on J-STAGE: March 31, 2008
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    In order to study the enzymatic properties of the δ-ornithine acylase in KT 801 (Pseudomonas sp.), experiments were carried out with the purified enzyme preparation. This enzyme has a pH optimum around 8.2 toward 5-N-benzoyl-L-ornithine. It is inhibited by Co2+, Zn2+, Fe3+, Cu2+, Hg2+, EDTA, and o-phenanthroline. The inactivation for EDTA is reversed by addition of Ca2+ or Mn2+ after dialysis. Km value toward 5-N-benzoyl-L-ornithine was calculated to be 1.8×10-4M. As a results of the investigation of substrate specificity, it was found that this enzyme hydrolyses not only L form of 5-N-benzoylornithine, but D form in the rate of about one sixth. The ratio of the activities toward L and D form remained constant all through the purification steps. These result strongly suggest that one enzyme has the both activities. Also, susceptible substrate to δ-ornithine acylase require absolutely the presence of a free carboxyl group, the presence of a free α-amino group is desirable for ready susceptibility of the substrate, but it is not an absolute requirement, and the susceptibility are considerably affected by carbon chain length between the carboxyamide group and the free carboxyl group. This enzyme shows no α-amino acylase activity. On the other hand, δ-ornithine acylase is quantitatively released when EDTA-lysozyme spheroplasts are made. From these result, it has been proposed that δ-ornithine acylase of KT 801 is at the cell surface.
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  • Keijiro Takagi, Tokuji Suzuki, Yukiya Saitoh
    1967 Volume 15 Issue 10 Pages 1597-1603
    Published: October 25, 1967
    Released on J-STAGE: March 31, 2008
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    The effect of terephthalic acid on the blood level of sulfaethylthiadiazole in the rabbit was examined. About twice increase of the biologic half-life of sulfaethylthiadiazole in the range of 50 to 150mg./kg. of terephthalic acid was shown at the simultaneous oral administration. No marked effect was shown by parenteral administration of terephthalic acid. The acute toxicity following simultaneous intraperitoneal administration was investigated in the mouse. The increase of the acute toxicity was not observed significantly judging from LD50 determined by the single administration of sulfaethylthiadiazole and of terephthalic acid.
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  • Hisashi Miyazaki, Yasuo Minaki, Yoshio Yoshimura
    1967 Volume 15 Issue 10 Pages 1604-1606
    Published: October 25, 1967
    Released on J-STAGE: March 31, 2008
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  • Hans Bohrmann, Egon Stahl, Hiroshi Mitsuhashi
    1967 Volume 15 Issue 10 Pages 1606-1608
    Published: October 25, 1967
    Released on J-STAGE: March 31, 2008
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  • Shigeharu Inouye
    1967 Volume 15 Issue 10 Pages 1609-1617
    Published: October 25, 1967
    Released on J-STAGE: March 31, 2008
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