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TSUNEHIRO KITAGAWA, TAKAKO MIURA, HIROKO KUROSE
1979 Volume 27 Issue 11 Pages
2551-2556
Published: November 25, 1979
Released on J-STAGE: March 31, 2008
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Conformational analyses of acetylated derivatives of viomycin were performed by proton magnetic resonance (PMR) and circular dichroism (CD) spectroscopic methods. All of the acetylviomycins showed α-methine chemical shift values over a wide region from 4.21 to 4.98 ppm, suggesting that all of the acetyl derivatives possess a rigid conformation at the sixteen-membered ring, as in viomycin. The amino acid derivatives of viomycin showed similar profiles of PMR and CD spectra. These derivatives were thus assumed to retain the rigid conformation. 1-Guanylviomycin, with a strongly basic group at the 1-position, was prepared, and was also found to possess a similar rigid conformation. The antimicrobial activities of 1-guanylviomycin and the acylated derivatives of viomycin toward Gram-positive and Gram-negative bacteria suggested that the rigid conformation is a necessary but not sufficient condition for activity. 1-Guanylviomycin showed antimicrobial activity similar to that of viomycin, confirming the previous conclusion that the two basic groups in viomycin are important for the antimicrobial activity. It was also concluded that the distance between the two basic groups is not critical.
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TSUGIO SHIMAMOTO, HIROYUKI MIMA, MASAYUKI NAKAGAKI
1979 Volume 27 Issue 11 Pages
2557-2563
Published: November 25, 1979
Released on J-STAGE: March 31, 2008
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The interactions of methyl and propyl p-hydroxybenzoate with polyethylene glycol (PEG) 4000 were investigated by means of an ultrafiltration technique. The results show that the interaction is a weak and nonspecific process of large binding capacity, and is a type of partitioning phenomenon between the macromolecule and the aqueous phase. The characteristics of this interaction are quite similar to those of the binding of p-hydroxybenzoates with the polyoxyethylene region of polyoxyethylene dodecyl ether (PDE) micelles. A solubility study of p-hydroxybenzoates in aqueous solutions of PEG-400 was also performed. Assuming that the increase in solubility of the preservatives in the presence of PEG was due to the interaction with PEG, the ratio of bound preservative concentration to PEG concentration was calculated. The ratio increased as the concentration of PEG in the solvent increased, and this was thought to be due in part to a dehydrating effect. A comparison of solubility data with the binding parameters of p-hydroxybenzoates for the secondary binding sites of PDE micelles provided information concerning the micellar hydration. The amount of water trapped by nonionic surfactant micelles was estimated and the values thus obtained were consistent with those reported elsewhere.
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HIDETO MATSUDA, HIDEKO ISHIHARA, SETSUZO TEJIMA
1979 Volume 27 Issue 11 Pages
2564-2569
Published: November 25, 1979
Released on J-STAGE: March 31, 2008
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The title trisaccharide (16) is a constituent of the higher oligosaccharides in human milk. As part of our program of synthesis of oligosaccharides in human milk, the title trisaccharide was prepared. Heating of a mixture of 1, 6-anhydro-2, 2´, 3, 3´, 4´-penta-O-benzyl-β-lactose and 2-methyl-(3, 4, 6-tri-O-acetyl-1, 2-dideoxy-α-D-glucopyrano) [2, 1-d]-2-oxazoline in nitromethane-toluene in the presence of p-toluenesulfonic acid at 95° for 1 hr with stirring afforded the protected 1, 6-anhydro-β-derivative of 16 (6). The protecting groups of 6 were removed by catalytic hydrogenation followed by deacetylation, or vice versa, to afford the 1, 6-anhydro-β-derivative of 16 (9). Compound 9 gave a crystalline peracetate (14). The 1, 6-anhydro-β-ring of 14 was cleaved by mild acetolysis to afford an anomeric mixture of the peracetate of 16, from which the α-anomer (15) was isolated as needles. Deacetylation of 15 gave the title trisaccharide as a hygroscopic amorphous powder.
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YOSHIHIKO INAMORI, YOSHIAKI KATO, KAZUHIRO MORIMOTO, KATSUAKI MORISAKA ...
1979 Volume 27 Issue 11 Pages
2570-2576
Published: November 25, 1979
Released on J-STAGE: March 31, 2008
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To delineate the time of onset and the mechanism of delayed toxic effects produced by streptothricin antibiotics in rats, the tissue antibiotic distribution, histopathologic features of the kidney, serum biochemical changes and antibiotic metabolites recovered in the urine after administration of a radiolabeled compound were investigated. Rats showed a pattern of tissue antibiotic distribution similar to that observed in the mouse. Microscopic examination of the kidney revealed lesions which became evident at 48 hr after the injection. Serum biochemical tests showed a rapid elevation of blood urea nitrogen and creatinine nitrogen levels from 48 hr post injection, with abnormalities in the cellulose acetate membrane electrophoresis pattern of serum proteins. Thus, nephrotoxic effects evoked by the antibiotic became evident about 48 hr after the injection, indicating that the time of onset of delayed toxicity of the compound is approximately 48 hr after dosing. As for the mechanism of the delayed toxic effects, evidence has been obtained for the formation of a toxic metabolite with an opened lactam ring, or an"acid compound"excreted in the rat urine. These findings support our previous inference, based on studies in mice.
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YOSHINORI KIDANI, YOICHI ASANO, MASAHIDE NOJI
1979 Volume 27 Issue 11 Pages
2577-2581
Published: November 25, 1979
Released on J-STAGE: March 31, 2008
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Pt (II) complexes of 4-substituted o-phenylenediamine (opda-R ; R=CH
3, OCH
3, H, Cl, COOH, NO
2, and SO
3H), PtX
2 (opda-R), were synthesized and tested for antitumor activity against P-388 leukemia. The infrared spectra of those complexes were analyzed to assign the Pt-N stretching vibrations on the basis of the halogeno trans effect and Hammett's σ values. The assigned Pt-N strectching vibrations were related to the antitumor activities of the opda-R Pt (II) complexes.
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SEIICHI TAKANO, NOBORU KUBODERA, HIROMITSU IWATA, KUNIO OGASAWARA
1979 Volume 27 Issue 11 Pages
2582-2588
Published: November 25, 1979
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The synthesis of a new prostaglandin synthon (14) from 5-trichloromethyl-4-oxatricyclo [4. 3. 0. 0
3, 7] non-8-ene (2) and its conversion to prostaglandin F
2α (21) are described. Compound (2) was transformed into the acetylene derivative (5) which was then led to the C-9 acetylene lactone (14) via a 6-step, 8-stage reaction. A new synthesis of (±)-prostaglandin F
2a (21) was completed through a 5-step reaction starting from the C-9 lactone (14).
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HIDEAKI NATSUGARI, KANJI MEGURO, YUTAKA KUWADA
1979 Volume 27 Issue 11 Pages
2589-2595
Published: November 25, 1979
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2-Amino-6-phenyl-3, 4-dihydro-1, 5-benzodiazocine derivatives (4) were synthesized by cyclization of 3-(2-amino-α-phenylbenzylideneamino) propionitriles (3). The reactivity of the diazocine (4a) was different from that of the structurally similar diazepine (6). Reaction of 4a with methylamine hydrochloride or with methanolic hydrogen chloride did not give the diazocine (9 or 11) but afforded the aminoethylquinazoline (10). The ultraviolet spectra indicated that the conjugation systems of 4a and 6 are different. Deuterium exchange reactions of 4a and 6 confirmed the presence of the equilibria 4a⇌4´a and 6⇌6´.
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AKIHIRO OHTA, KAZUKO HASEGAWA, KATSUYO AMANO, CHIHARU MORI, AKIKO OHSA ...
1979 Volume 27 Issue 11 Pages
2596-2601
Published: November 25, 1979
Released on J-STAGE: March 31, 2008
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Irradiation of several 2-(β-arylvinyl) pyrazines at room temperature using a high pressure mercury lamp afforded aza-phenanthrenes in moderate yields. The ring closure of 2-[β-(3-pyridyl) vinyl] pyrazine (IIIb) occurred only at the 4-position of the pyridine ring, whereas 2-[β-(2-naphthyl) vinyl] pyrazine (IIIe) cyclized at the 1-position of the naphthalene ring. 2, 5-Distyrylpyrazine (VIa) and 2, 5-bis [β-(2-pyridyl) vinyl] pyrazine (VIb) were also irradiated in refluxing benzene to give dibenzo [a, h] phenazine (XVI) and dipyrido [3, 2-α : 3´, 2´-h] phenazine (XVII), respectively.
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TSUGIO SHIMAMOTO, HIROYUKI MIMA
1979 Volume 27 Issue 11 Pages
2602-2607
Published: November 25, 1979
Released on J-STAGE: March 31, 2008
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The effect of polyols, i.e., glycerol, propylene glycol and 1, 3-butylene glycol, on the interaction between p-hydroxybenzoates and polyoxyethylene (15 units of oxyethylene) dodecyl ether was investigated by an ultrafiltration technique using a Diaflo membrane. Polyols had little effect on the binding of p-hydroxybenzoate to the primary class of sites in the nonionic surfactant micelles. In this binding process, bound preservative molecules are thought to be located at the oxyethylene-hydrocarbon interface, so it seems possible that polyols added to the system were too hydrophilic to penetrate deeply into the micelles and to compete effectively with this class of bound preservative. However, polyols modified the binding to the secondary class of sites to some extent ; namely, these compounds could displace a part of the bound preservative from the polyoxyethylene region of the micelles. 1, 3-Butylene glycol was the most effective polyol ; glycerol was somewhat less effective in enhancing the preservative activity.
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HIDEAKI NATSUGARI, KANJI MEGURO, YUTAKA KUWADA
1979 Volume 27 Issue 11 Pages
2608-2617
Published: November 25, 1979
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When 2-amino-3, 4-dihydro-6-phenyl-1, 5-benzodiazocines (1) and 2-amino-5-phenyl-3H-1, 4-benzodiazepines (5) were treated with m-chloroperbenzoic acid, oxidation occurred selectively at the 1-position giving the corresponding 1-oxides (2 and 6), which are a novel class of derivatives of the diazocines and the diazepines. Although reaction of 2 with phosgene afforded the oxadiazolone derivative (4) in high yield, rearrangement of the diazepine oxide (6) occurred upon treatment with phosgene in the presence of imidazoles to form the 3-imidazolyl compound (9). When 6a was treated with acetic anhydride, rearrangement also occurred to give the 3-oxo compound (8).
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HIDEAKI NATSUGARI, YUTAKA KUWADA
1979 Volume 27 Issue 11 Pages
2618-2626
Published: November 25, 1979
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The reaction of 2-amino-1, 5-benzodiazocine 1-oxides (1) with acetylenecarboxylates (2, 11) afforded C
(10)-alkylated derivatives (3) via 3, 3-sigmatropic rearrangement. Compounds 3 gave 10-alkoxycarbonylmethyl-1, 5-benzodiazocines (4) when heated in ethanol. Heating of 3a-e in pyridine, on the other hand, gave indole derivatives (9), which were converted into 7-benzoylindoles (10a-e) by acid hydrolysis. The reaction of 2-amino-1, 4-benzodiazepine 1-oxides (13) with acetylenedicarboxylates (11) also gave the rearranged products (14).
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AKIHIRO OHTA, TERUO KURIHARA, HIROKO ICHIMURA, TOKUHIRO WATANABE
1979 Volume 27 Issue 11 Pages
2627-2635
Published: November 25, 1979
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Seven mononitroquinolines were nitrated to yield dinitroquinolines. It was found that the nitration occurred in the benzene portion of the mononitroquinolines, and at a carbon with comparatively large values of q
r. f
r(E), and S
r(E), except in the case of 5-nitroquinoline (IV).
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YOSHIHIRO HARIGAYA, TSUTOMU SUZUKI, MASAYUKI ONDA
1979 Volume 27 Issue 11 Pages
2636-2641
Published: November 25, 1979
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The lactone (5) reacts with methylamine to afford the methylaminophthalide (6). On the basis of the reactions of 6 and related compounds, the spiro lactam (14) is suggested to be an intermediate in the formation of 6 from 5.
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HIROSHI YAMANAKA, SETSUKO NIITSUMA, TAKAO SAKAMOTO
1979 Volume 27 Issue 11 Pages
2642-2646
Published: November 25, 1979
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Like pyridine 1-oxide, 4-ethyl-6-methylpyrimidine 1-oxide reacts with phenyl isocyanate ; the products in the latter case are 2-anilino-4-ethoxy-6-methylpyrimidine and 1, 3-diphenyl-1-(4-ethoxy-6-methyl-2-pyrimidinyl) urea. In contrast to this reaction, phenyl isothiocyanate transformed the same N-oxide into 7-methyl-3-phenyl-2, 3-dihydrooxazolo [4, 5-d] pyrimidine-2-thione.
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MORIO IKEHARA, HIROKO MIKI, AKIRA HASEGAWA
1979 Volume 27 Issue 11 Pages
2647-2652
Published: November 25, 1979
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5´-Deoxyadenosine (I) was brominated at the 8-position and converted to 8, 2´-(VI) and 8, 3´-S-cyclonucleosides (VII) via the 2´, 3´-dibutylstannylene compound by successive tosylation and heating with NaSH. When VI was treated with tert-butyl hypochlorite, an exo sulfoxide VIII was obtained. Desulfurization of VI and VII with Raney Ni gave 2´, 5´-(IX) and 3´, 5´-dideoxyadenosine (X), respectively. An 8, 2´-O-cyclonucleoside (XII) was also obtained from V by a standard procedure. Rearrangement of XII to a ribo-type epoxide (XIII) in the presence of 0.1 N NaOH was observed.
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TAKAO SAKAMOTO, SETSUKO NIITSUMA, MICHINAO MIZUGAKI, HIROSHI YAMANAKA
1979 Volume 27 Issue 11 Pages
2653-2660
Published: November 25, 1979
Released on J-STAGE: March 31, 2008
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N-Oxidation of pyrimidines having unsymmetrically substituted 4-and 6-positions with hydrogen peroxide in acetic acid gave mixture of their 1-oxides and 3-oxides. Ring transformation of these 1-oxides and 3-oxides into isoxazoles occurred on treatment with mineral acid, and provided information on the position of the N-oxide group in the pyrimidine N-oxides. Nuclear magnetic resonance spectroscopy with a lanthanide shift reagent was also found to be useful in identifying the pyrimidine 1-and 3-oxides.
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KIMIHIRO YOSHIMOTO, KAZUKO TAHARA, SHIGEYUKI SUZUKI, KAZUMI SASAKI, YO ...
1979 Volume 27 Issue 11 Pages
2661-2674
Published: November 25, 1979
Released on J-STAGE: March 31, 2008
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All isomeric 1α-, 1β-, 2-, 3-, 4-, and 6-mono-O-acyl-D-glucopyranoses (acyl group from caprinoyl through stearoyl) were synthesized in a regio-(and stereo-) selective manner. Gas-liquid chromatography (trimethylsilyl (TMS) derivatives), infrared, and
1H-nuclear magnetic resonance data, which provided evidence for assignment of the position of the acyl chain, are described. Compounds previously reported to be 2-O-acyl and 3-O-acyl-D-glucoses were shown to be 6-O-acyl derivatives. In the 3-and 6-O-acyl derivatives, anomerization was slow and they were present largely as α-anomers, while the 2-and 4-O-acyl derivatives were mixtures of α-and β-anomers due to their rapid anomerization. Some di-O-acyl-D-glucopyranoses (1β, 6-, 2, 3-, and 4, 6-) and a new tri-O-acyl-D-glucopyranose (2, 4, 6-) were also prepared, all of them except for the 1β, 6-di-O-acyl derivative were obtained as α-anomers.
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JUNICHI TANI, YOSHIHISA YAMADA, TAKASHI OCHIAI, RYUICHI ISHIDA, ICHIZO ...
1979 Volume 27 Issue 11 Pages
2675-2687
Published: November 25, 1979
Released on J-STAGE: March 31, 2008
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A number of derivatives of 6-amino-2-fluoromethyl-3-(o-tolyl)-4 (3H)-quinazolinone (15), a potent muscle relaxant, have been prepared and screened in terms of the loss of righting reflex test and the rotating rod test in mice. Several derivatives with additional fluorine substitution or with repositioning of the fluorine atom exhibited high activities. Other structural modifications included acylation, carbamoylation, and alkoxycarbonylation of the 6-amino group, hydroxylation at the 3-tolyl group, and replacement of the fluorine atom at the 2-fluoromethyl group by oxygen, nitrogen, and sulfur nucleophiles ; these modifications all resulted in loss of activity.
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MASAKO MAEDA, AKIO TSUJI
1979 Volume 27 Issue 11 Pages
2688-2694
Published: November 25, 1979
Released on J-STAGE: March 31, 2008
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Nickel (II) and copper (II) complexes of amino sugars (glucosamine, galactosamine, and mannosamine) derived from salicylaldehyde or its derivatives have been newly synthesized and characterized. In these metal complexes, the Schiff bases are tridentate, the nickel (II) complexes are octahedral, and the copper (II) complexes are tetrahedral or pseudotetrahedral except for Cu (II) (N-salicylidene mannosamine)
2, which is nearly planar. The nickel (II) and copper (II) complexes of N-salicylidene mannosamine show electronic spectra, magnetic moments, and circular dichroism spectra which are different from those of the complexes of N-salicylidene glucosamine and -galactosamine.
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YUKINOBU IKEYA, HEIHACHIRO TAGUCHI, ITIRO YOSIOKA, HIROSHI KOBAYASHI
1979 Volume 27 Issue 11 Pages
2695-2709
Published: November 25, 1979
Released on J-STAGE: March 31, 2008
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Four new dibenzocyclooctadiene lignans, gomisins N (1), O (2) and E (4), and epigomisin O (3), together with a known lignan (+)-deoxyschizandrin (5) were isolated from the fruits of Schizandra chinensis BAILL. (Schizandraceae). The structures of the new lignans were elucidated by chemical and spectral studies. The transformation of 1 to deangeloylgomisin B (debenzoylgomisin C) (6) is also described.
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FUJIO KAMETANI, SHUJI KITAGAWA, KEITARO NISHIYAMA
1979 Volume 27 Issue 11 Pages
2710-2717
Published: November 25, 1979
Released on J-STAGE: March 31, 2008
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The reverse permeation of Mn
2+ across a cellulose membrane in CaCl
2-MnCl
2-H
2O and NaCl-MnCl
2-H
2O systems was studied. The reverse permeation of an ion is described by equation (1) which consists of two terms, i.e., the electric potential gradient and concentration gradient terms. When the flux of an ion due to the electric potential gradient is large and opposite in direction to that due to the concentration gradient, reverse permeation can occur, i.e., concentration of the solute into the compartment with higher concentration. In both systems, Mn
2+ (even at low concentrations) was concentrated in one compartment of the permeation cell by reverse permeation. The concentration of Mn
2+ was more effective in the presence of Ca
2+ than Na
+. The experimental values were in good agreement with Guntelberg's approximations.
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TAKEO KOBAYASHI, TETSUO HIRAOKA
1979 Volume 27 Issue 11 Pages
2718-2726
Published: November 25, 1979
Released on J-STAGE: March 31, 2008
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Treatment of 7β-sulfenamidocephalosporins 7 with an oxidizing agent such as active manganese dioxide gave the sulfenimines 8, which were easily methoxylated to the 7α-methoxy-sulfenamides 9 with lithium methoxide. The 7α-methoxy-sulfenamidocephalosporins 9 were converted to the free amine 10 by reaction with sodium iodide. Acylation of 10 afforded the cephamycin derivative 11. This method was also successfully applied to the penicillin series, leading to the sulfenimine 13, which was methoxylated to furnish the desired 6α-methoxy-penicillin 14 together with the ring-opened product 15.
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TAKEO KOBAYASHI, KIMIO IINO, TETSUO HIRAOKA
1979 Volume 27 Issue 11 Pages
2727-2734
Published: November 25, 1979
Released on J-STAGE: March 31, 2008
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The sulfinamides 3 were transformed to sulfenimines 4 by treatment with thionyl chloride and a weak base such as quinoline (or triethylamine). The sulfenimines 4 were methoxylated with lithium methoxide to give 7α-methoxysulfenamides 5, which were directly acylated with an acyl chloride to furnish cephamycin derivatives 6. There was a major difference between the acylation of 7α-methoxysulfenamides 5 and that of the 7α-H derivatives 7. Reduction of the imines 4a with metal hydrides gave 7β-sulfenaminocephalosporins 12 together with a small amount of the 7α-isomers 13. The synthetic sequence 4a→12→14 provides a useful method for the isomerization of 7α-aminocephalosporins 17 to the corresponding 7β-isomers 18.
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SUMIRO ISODA, MIYOSHI HIRATA
1979 Volume 27 Issue 11 Pages
2735-2742
Published: November 25, 1979
Released on J-STAGE: March 31, 2008
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To investigate the structure-activity relationship between two isomers of 4-aminomethylcyclohexanecarboxylic acid (AMCHA) in connection with their antiplasmin activity, their conformations in H
2O were simply estimated on the basis of conformational free energy (-⊿G°). The nuclear magnetic resonance spectra of both isomers of 4-tertbutylcyclohexylmethylamine hydrochloride and of cyclohexylmethylamine hydrochloride gave a value of -⊿G°=1.4 kcal/mol for the N^
+H
3CH
2-group. The biologically active trans AMCHA in H
2O exists, as in its crystal structure, largely in the equatorial N^
+H
3CH
2-equatorial COO-form, while about 79% of cis AMCHA exists as the axial N^
+H
3CH
2-equatorial COO-form, in contrast to the crystal structures of its hydrohalides. Further, 1-Me AMCHA, 4-Me AMCHA and 4-(1-aminoethyl) cyclohexanecarboxylic acid were synthesized. The stereoisomers of these compounds were separated and the configurations of the isomers were determined. No compound showed a more potent antiplasmin activity than trans AMCHA.
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TSUGIO SHIMAMOTO, HIROYUKI MIMA
1979 Volume 27 Issue 11 Pages
2743-2750
Published: November 25, 1979
Released on J-STAGE: March 31, 2008
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A simple mathematical model was derived to evaluate the antimicrobial activity of p-hydroxybenzoates in emulsified systems containing nonionic surfactants of the polyoxyethylene type. The model consists of preservative bound within the surfactant micelles, species partitioned into the oil phase, the ionized form in the water phase and the free effective form in the aqueous phase. The validity of the derived equations was confirmed by means of ultrafiltration experiments. The total concentration of a preservative necessary to give the desired concentration of free preservative in the aqueous phase of the emulsion can be calculated using this model. It was also shown that the amount of bound preservative within a mixture of several surfactants could be predicted from the binding parameters which characterize the interaction with each surfactant constituting the mixture, and that the binding parameters of a preservative for a surfactants mixture could be estimated from the hydrophile-lipophile balance value of the mixture and the binding parameters of some appropriate surfactants. The limitations of this simple mathematical model are discussed.
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ATSUSHI WATANABE, SABURO TASAKI, YOSHIKAZU WADA, HIDEO NAKAMACHI
1979 Volume 27 Issue 11 Pages
2751-2759
Published: November 25, 1979
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The content of water of crystallization in the phase II modification of thiamine hydrochloride has not previously been definitely determined. This is widely thought to be an anhydrous form, since it does not show any weight change on drying at 105° for 2hr. The present work describes the crystal structure of the phase II modification of thiamine hydrochloride crystals. It was found to be a hemihydrate and to be stable under normal conditions both in the solid state and in suspension in a saturated solution.
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SHUNICHI HASHIMOTO, KENJI KOGA
1979 Volume 27 Issue 11 Pages
2760-2766
Published: November 25, 1979
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A novel method was devised for the asymmetric synthesis of 2-alkylcycloalkanones (10) by metalation and alkylation of chiral cyclic imines (8), using an optically active α-amino acid tert-butyl ester (7) as a chiral source. The present method provides 2-alkylcycloalkanones (10) of unequivocally predictable absolute configuration in quite high enantiomeric purities, allowing easy recovery of the chiral reagent without any racemization for reuse. The present method is also shown to be applicable for the creation of an asymmetric quaternary carbon atom, as exemplified in the synthesis of 2-methyl-2-phenylcycloalkanones (13). The mechanism of the reaction is proposed.
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FAROUK H. AL-HAJJAR, YUSUF A. AL-FARKH, HAYAT S. HAMOUD, YUSUF AL-SULT ...
1979 Volume 27 Issue 11 Pages
2767-2774
Published: November 25, 1979
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1, 3-Diaryl-2-propen-1-ones (IIa, b) reacted with methyl α-naphthylacetate (Ib) in the presence of sodium methoxide at room temperature, or under reflux to give only the corresponding 4, 6-diaryl-3-[3^
-(1^
-3^
-diarylpropan-1^
-one)]-3-α-naphthyl-4-hydro-2H-pyran-2-ones (IIIa, b). However, on reacting the ketones (IIc-f) with ethyl phenylacetate (Ia) in the presence of sodium ethoxide at room temperature, or under reflux, the corresponding ethyl γ-aroyl-β-aryl-α-phenyl-butyrates (IVa-d) or 4, 6-diaryl-3-[3^
-(1^
-, 3^
-diarylpropan-1^
-one)]-3-phenyl-4-hydro-2H-pyran-2-ones (IIIc, d), respectively, were obtained. The reaction of these compounds, (III) and (IV), with hydrazine hydrate gave the corresponding (3H)-1, 2-diazepin-3-one (VI) and hydrazone (IX) derivatives, respectively. The structures of the products were established by chemical and spectroscopic evidence.
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HITOSHI NAKAYAMA, MASAYUKI NOZAWA, YUICHI KANAOKA
1979 Volume 27 Issue 11 Pages
2775-2780
Published: November 25, 1979
Released on J-STAGE: March 31, 2008
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Photolysis of some amido derivatives of nitrophenyl azides was studied. In most cases, the products isolated were azo compounds and primary amines formed via triplet nitrenes. However, an anthranil, an intramolecular insertion product of nitrene into the adjacent amido group, was a major product in the case of o-amidonitrophenyl azide. A quenching study using isoprene showed that anthranil is formed from a singlet nitrene. The reaction modes of the nitrophenyl azides and the applicability of the compounds as potential photoaffinity labels are discussed.
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YUKIHISA KURONO, TORU MAKI, TOSHIHISA YOTSUYANAGI, KEN IKEDA
1979 Volume 27 Issue 11 Pages
2781-2786
Published: November 25, 1979
Released on J-STAGE: March 31, 2008
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In order to investigate the reactivity of human serum albumin (HSA) with ester-type drugs and to characterize the site of the esterase-like activity, the Michaelis constants (Ks) and the catalytic rate constants (k
cat) were determined for the reactions of phenyl acetates and p-nitrophenyl esters with HSA at 25°. A linear relationship between log k
cat and Hammett σ-values was found for phenyl acetates at pH 9.9 ; its slope was +1.52. It is suggested that aspirin also reacts with HSA by the same mechanism. The effects of aromatic substituents on the K
s values were small. The K
s values for p-nitrophenyl esters at pH 7.0 were correlated with Hansch's π and Taft's E
s values as follows ; log K
s=-0.578 π-0.184 E
s-3.566 (γ=0.963). The hydrophobic interaction was predominant in the binding of the substrates to HSA. The log k
cat-pH profile obtained for p-nitrophenyl acetate indicates the participation of a single catalytic group, pK
a≒9.5, in this reaction.
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SOJI SUGAI, KAZUO TOMITA
1979 Volume 27 Issue 11 Pages
2787-2794
Published: November 25, 1979
Released on J-STAGE: March 31, 2008
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The reaction of 2-methyl-5-phenyl-3-phenylthioisoxazolium chloride (IIa) with a mixture of optimum amounts of thiophenol (2 eq.) and triethylamine (TEA) (1 eq.) gave benzoylketene S, N-acetal (IIIa) in maximum yield. To determine the reaction mechanism, IIa was treated with tri-n-butylphosphine in the presence of acetic acid (AcOH) to afford N-acetyl-N-methylbenzoylacetamide (VIII). The isolation of VIII provides evidence for the involvement of an intermediate, benzoylketene N-methylimine (VII), in the transformation of IIa to IIIa. Various acylketene S, N-acetals (III) were synthesized by the reaction of 3-chloroisoxazolium chlorides (I) with mixtures of optimum amounts of thiols (3 eq.) and TEA (2 eq.). On the other hand, the S, N-acetal (IIIj) was also prepared by the reduction of 3-ethylthio-2, 5-dimethylisoxazolium iodide (XIII) with zinc in AcOH. Cyclization of IIIj with hydroxylamine or hydrazine afforded 3-methylaminoisoxazole (XIV) or 3-methylaminopyrazole (XV) in good yield.
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MITSURU FURUKAWA, TADASHI OKAWARA, YOSHIHIDE NOGUCHI, YURIKO TERAWAKI
1979 Volume 27 Issue 11 Pages
2795-2801
Published: November 25, 1979
Released on J-STAGE: March 31, 2008
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Asymmetric synthesis of optically active β-amino-α, α-dimethyl-β-phenylpropionic acid (7) was achieved by the reaction of chiral Schiff bases with dimethylketene or with Reformatsky reagent, in the range of 33-35% optical purities. The specific rotation and configuration of 7 were determined by correlation with authentic R (+)-β-benzoylamino-α, α-dimethyl-β-phenylethanol. The steric courses of these reactions are discussed.
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TERUAKI YUZURIHA, KOUICHI KATAYAMA, JUNZO TSUTSUMI, MASAMI KIMURA
1979 Volume 27 Issue 11 Pages
2802-2806
Published: November 25, 1979
Released on J-STAGE: March 31, 2008
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Three immunological methods (radioimmunoassays and enzymoimmunoassay) were established for the sensitive and specific measurement of human lysozyme in biological fluids. Using these methods, human lysozyme was determined in the concentration range of 5 to 250 ng/ml. Although radioimmunoassay with dextran-coated charcoal offered the best precision, enzymoimmunoassay by the sandwich technique using microtiter plates was found to be the most convenient method, giving satisfactory precision and reproducibility.
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THORU ENDO, HEIHACHIRO TAGUCHI, HIROSHI SASAKI, ITIRO YOSIOKA
1979 Volume 27 Issue 11 Pages
2807-2814
Published: November 25, 1979
Released on J-STAGE: March 31, 2008
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Three glycosides named hydroxy-β-ionone glucoside (1), aeginetoside (2) and isoaucubin (3) were isolated from the n-butanol extract of Aeginetia indica L. var. gracilis NAKAI. The structures of 1, 2 and 3 were elucidated by chemical and spectral studies.
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TOSHIAKI MIURA, TAKETO OGISO
1979 Volume 27 Issue 11 Pages
2815-2819
Published: November 25, 1979
Released on J-STAGE: March 31, 2008
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Rat erythrocytes were incubated in the photoactivated riboflavin system, in which the formation of erythrocytes resistant to hypotonic hemolysis occured. Cells illuminated for 60 min were as sensitive to hypotonic hemolysis as unilluminated cells. In contrast, cells illuminated for 120 min showed complete resistance to hypotonic hemolysis. Experiments with catalase, superoxide dismutase and other radical scavengers showed that the formation of protected cells appears to be due to H
2O
2 generated in the photoactivated riboflavin system. Microscopic examination revealed that cells exposed to O
2-for 120 min were enlarged and contained more intensely intracellular materials around the interior periphery. These results suggest that rigid cells resistant to hypotonic hemolysis may be formed by H
2O
2 oxidation of hemoglobin and membrane elements of the cells.
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ATSUKO NODA, KENJI MATSUYAMA, SHUHWAI YEN, KEIZO SOGABE, YOSHINORI ASO ...
1979 Volume 27 Issue 11 Pages
2820-2826
Published: November 25, 1979
Released on J-STAGE: March 31, 2008
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Tetrazolo [5, 1-α] phthalazine (Tetra-P) was detected by GC and GC-MS in extracts of incubation mixtures of hydralazine (HP) in human saliva with simulated gastric juice (SGJ), while 3-methyl-s-triazolo [3, 4-α] phthalazine (MTP) and s-triazolo [3, 4-α] phthalazine (Tri-P) were identified as the main products in the absence of SGJ. Tetra-P was also found in rabbit urine when an aqueous solution of NaNO
2 was given before and after the oral administration of HP. The amounts of MTP, Tri-P and Tetra-P formed depended on the pH and incubation time.
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TAKASHI ABIKO, MIHOKO KUMIKAWA, HIROSHI SEKINO
1979 Volume 27 Issue 11 Pages
2827-2831
Published: November 25, 1979
Released on J-STAGE: March 31, 2008
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The glucagon fragment H-Phe-Val-Gln-Trp-Leu-Met-Asn-Thr-OH (positions 22-29) was synthesized by a conventional method. Two glucagon fragments, H-His-Ser-Gln-Gly-Thr-Phe-Thr-Ser-Asp-Tyr-Ser-Lys-Tyr-Leu-OH (positions 1-14) and the octapeptide fragment synthesized in this study were tested for inhibitory activity towards glucose-6-phosphate dehydrogenase. The octapeptide (positions 22-29) inhibited glucose-6-phosphate dehydrogenase activity by 18% at a concentration of 0.5 mg/ml.
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RYOKO ABE, ATSUKO FUKUHARA, SHIRO MORIMOTO
1979 Volume 27 Issue 11 Pages
2831-2834
Published: November 25, 1979
Released on J-STAGE: March 31, 2008
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Changes in reference enzyme activities of subcellular particles of the rat kidney cortex were followed during periods of sodium restriction. Animals were maintained on a sodium-deficient diet for 28 days. Dietary sodium deprivation resulted in a marked decrease in daily urinary excretion of sodium and potassium from the second day, although the urine volume did not change significantly. The kidney cortex homogenate of sodiumrestricted rats was analyzed for the activities of reference enzymes. Acid phosphatase (lysosomal enzyme) and succinate dehydrogenase (mitochondrial enzyme) activities, and protein concentration remained unchanged throughout the experimental period. However, increases in the specific activities of glucose-6-phosphatase (microsomal enzyme), D-amino acid oxidase and catalase (peroxisomal enzymes) were observed after the 7th day of experiments.
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MASAHIRO NAKANO, KAORI TAKIKAWA, KAZUHIKO JUNI, TAKAICHI ARITA
1979 Volume 27 Issue 11 Pages
2834-2837
Published: November 25, 1979
Released on J-STAGE: March 31, 2008
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The possible use of konjac gels to achieve sustained release of theophylline on oral administration was examined in vitro. Theophylline was trapped in the gels by soaking the gels in a hot drug solution and subsequently drying them. Sustained release of the drug from the dried konjac gels was obtained. No marked difference was observed in the release patterns in the range of pH values expected in the gastrointestinal tract, and the drug contained in the gels was completely released.
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TAKU CHIBA, SETSUZO TEJIMA
1979 Volume 27 Issue 11 Pages
2838-2840
Published: November 25, 1979
Released on J-STAGE: March 31, 2008
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A new synthesis of α-L-fucose from D-glucose is described. The key intermediate is methyl 2, 3-di-O-acetyl-4, 6-O-benzylidene-α-D-altropyranoside (1), synthesized from methyl α-D-glucopyranoside by known procedures. Compound 1 was converted into methyl 2, 3-di-O-acetyl-4-O-benzoyl-6-bromo-6-deoxy-α-D-altropyranoside (2) by treatment with N-bromosuccinimide. Dehydrobromination of 2 afforded the 5, 6-unsaturated glycoside (4), which underwent reduction by hydrogen, mainly with inversion at C-5, to give methyl 2, 3-di-O-acetyl-4-O-benzoyl-6-deoxy-β-L-galactopyranoside (5) with a small amount of the isomeric methyl 2, 3-di-O-acetyl-4-O-benzoyl-6-deoxy-α-D-altropyranoside (3). The ratio of 3 to 5 was about 1 to 4. Deacylation of a mixture of 3 and 5 gave crystalline methyl β-L-fucopyranoside (6) and a syrupy methyl 6-deoxy-α-D-altropyranoside. Acidic hydrolysis of 6 afforded crystalline α-L-fucose in 19.3% yield from 1 via 5 steps.
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TOZO FUJII, SHIGEYUKI YOSHIFUJI, KYOKO IKEDA
1979 Volume 27 Issue 11 Pages
2841-2845
Published: November 25, 1979
Released on J-STAGE: March 31, 2008
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The Michael addition of diethyl malonate to 1-acetyl-3-ethyl-2, 3-dihydro-6 (1H)-pyridone (3) in EtOH at 55° has been found to give the trans isomer (4a) and the cis isomer (4b) of diethyl 5-ethyl-2-oxo-4-piperidinemalonate in a ratio of 85 : 15. The stereochemical assignments were based on C-13 nuclear magnetic resonance spectroscopic evidence as well as chemical interrelation with substances of known configuration. The latter included decarbethoxylation of 4a and 4b in dimethyl sulfoxide-H
2O-NaCl to give the lactam monoesters 5a and 5b, conversion of 4a into trans-1-benzyl-5-ethyl-2-oxo-4-piperidinemalonic acid (7a) through the lactim ether 9a and its benzylated product 8a, debenzylation of 7a with sodium in liquid ammonia to give 6a, and alkaline hydrolysis of 4a to 6a.
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TADAO SAKAI, NORIKO OHNO
1979 Volume 27 Issue 11 Pages
2846-2848
Published: November 25, 1979
Released on J-STAGE: March 31, 2008
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A new application of tetrabromophenolphthalein ethyl ester is reported for the determination of papaverine. The method is based on solvent extraction and utilization of the thermochromism of a red-colored charge transfer complex (TBPE·H·papaverine). Papaverine can be determined successfully and selectively even in the presence of quaternary ammonium salts by using the thermochromism caused by a temperature change in an organic solvent (1, 2-DCE). A linear plot was obtained in the concentration range (1-5)×10
-5M papaverine in the initial aqueous solution, with ΔA/Δt as the ordinate and the concentration as the abscissa.
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KAZUICHI HAYAKAWA, TOSHIO IMANARI, SHUKO ASAZUMA, RYOICHI KIZU, MOTOIC ...
1979 Volume 27 Issue 11 Pages
2849-2851
Published: November 25, 1979
Released on J-STAGE: March 31, 2008
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An effective method for fractional analysis of zinc in rabbit plasma was established, using polyethylene glycol. Rabbit plasma zinc was separated into two fractions ; the zinc profile in the precipitate showed two peaks, which were not albumin-bound zinc, on gel filtration, while the zinc in the supernatant proved to be albumin-bound zinc. The proposed method was used to investigate the effect of feeding on plasma zinc in rabbits. The decrease of total plasma zinc on feeding was significant, and was mainly due to that of albumin-bound zinc.
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SHIGEO IKEGAWA, YOSHIHIRO HINO, TOSHIO NAMBARA
1979 Volume 27 Issue 11 Pages
2852-2854
Published: November 25, 1979
Released on J-STAGE: March 31, 2008
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The stereochemistry of hydrogen loss at C-2 in the microbial transformation of 5β-pregnane-3, 11, 20-trione is described. Epimeric substrates stereospecifically labeled with deuterium at C-2 were incubated aerobically with Septomyxa affinis, and the biotransformation products, 5β-androst-1-ene-3, 11, 17-trione and 5β-androstane-3, 11, 17-trione, were separated. Inspection of their mass and nuclear magnetic resonance spectra showed that elimination of hydrogen at C-2 in Δ
1-dehydrogenation is stereoselectively β.
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NORIICHI ODA, TAISEI UEDA, ISOO ITO
1979 Volume 27 Issue 11 Pages
2855-2857
Published: November 25, 1979
Released on J-STAGE: March 31, 2008
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Nucleophilic substitution reactions of (ferrocenylmethyl) trimethylammonium iodide (1) with thiols lead to the corresponding (ferrocenylmethyl) thio compounds.
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HARUO SAIKACHI, TOKUJIRO KITAGAWA, HIDEAKI SASAKI
1979 Volume 27 Issue 11 Pages
2857-2861
Published: November 25, 1979
Released on J-STAGE: March 31, 2008
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The reaction of tosylmethyl isocyanide (7) with methyl propiolate (14a), dimethyl acetylenedicarboxylate (14b), methyl 3-(2-furoyl) propiolate (14c), and methyl 3-benzoylpropiolate (14d) in the presence of an equimolar amount of base at room temperature gave the corresponding 1 : 2 adducts, i.e., methyl 3-(1-pyrrolyl) acrylate derivatives (16a, 16b, 16c, and 16d, respectively) as final products. The temperature dependence of the reaction made it possible to isolate the pyrroles (15a and 15b), postulated as intermediates of the reaction, at low temperature.
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TAKEO HIGASHINO, TATSUHIKO KATORI, EISAKU HAYASHI
1979 Volume 27 Issue 11 Pages
2861-2864
Published: November 25, 1979
Released on J-STAGE: March 31, 2008
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Treatment of 3-substituted 3H-1, 2, 3-triazolo [4, 5-d] pyrimidines (I) with active methylene compounds, such as 1, 3-dicarbonyl compounds (A-1 to A-2), aliphatic ketones (A-3 to A-4), and cyclic ketones (A-5 to A-6), in the presence of dilute sulfuric acid gave the 3-substituted 3H-1, 2, 3-triazolo [4, 5-b] pyridines (IIIm-1 to IIIm-2, IIIm-5 to IIIm-6, and IIIp-1 to IIIp-6). The mechanism of the transformation is discussed.
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SHINJI FUNAYAMA, HIROSHI HIKINO
1979 Volume 27 Issue 11 Pages
2865-2868
Published: November 25, 1979
Released on J-STAGE: March 31, 2008
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The extract of a traditional Oriental medicine"kaki-yo, "Diospyros kaki leaves, was fractionated, monitoring for hypotensive activity against urethane-anesthetized rats ; astragalin and isoquercitrin were obtained as the active principles.
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MARIKO CHIBA, KAZUKO OKABE, SUEO HISADA, KATSUHITO SHIMA, TSUNEMATSU T ...
1979 Volume 27 Issue 11 Pages
2868-2873
Published: November 25, 1979
Released on J-STAGE: March 31, 2008
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The structure of a new lignan glucoside isolated from the stem of Olea europaea LINN. (Oleaceae) was elucidated as (+)-1-acetoxypinoresinol-4´-β-D-glucoside [(1S, 2R, 5R, 6S)-1-acetoxy-2-(3´-methoxy-4´-hydroxyphenyl)-6-(3"-methoxy-4"-hydroxyphenyl)-3, 7-dioxabicyclo [3, 3, 0] octane 4´-β-D-glucopyranoside] by analysis of the carbon-13 nuclear magnetic resonance and circular dichroism spectra.
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NOBUTOSHI TANAKA, HARUKA MAEHASHI, SUMIE SAITO, TAKAO MURAKAMI, YASUHI ...
1979 Volume 27 Issue 11 Pages
2874-2876
Published: November 25, 1979
Released on J-STAGE: March 31, 2008
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Aus den oberirdischen Teilen von Arachinoides standishii OHWI wurden 1-(2, 4, 6-Trimethoxybenzol)-but-2-en-1-on (I), 2-Methyl-5, 7-dimethoxychromanon (II), 2-Athyl-5, 7-dimethoxychromanon (III) und 1-(2-Hydroxy-4, 6-dimethoxy-benzol)-3-hydroxy-butan-1-on-3-O-β-D-allosid (IV) sowie ein neuartiges Sesquiterpen (V) mit Tetrahydroacenaphthen-Grundgerust isoliert und deren Strukturen aufgeklart, wobei II und III moglicherweise Artefakte darstellen.
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