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KENJI SUZUKI, YUSUKE SASAKI, NOBUYOSHI ENDO
1976 Volume 24 Issue 1 Pages
1-9
Published: January 25, 1976
Released on J-STAGE: March 31, 2008
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These tactics depend primarily on coupling of a highly polar compound, as a highly polar handle in the purification process, with the terminal amino group of the desired sequence assembled on a solid support. Lysine was used as the highly polar compound in this study. All protecting groups labile towards hydrogen fluoride were removed as usual and the resulting crude peptide was purified through a carboxymethyl cellulose column. The amino terminal lysine residue was removed by Edman degradation to obtain the desired peptide. The technique thus developed has permitted the syntheses of peptide fragments of the B chain of human insulin, H-Gly-Phe-Phe-Tyr-Thr-Pro-Lys (Tfa)-Thr-OH and H-Gly-Ser-His-Leu-Val-OH, with a simple purification process in good yield and in high purity.
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HIROSHI HOJO, YASUO SUZUKI, YOKO KONISHI, MITSURU UCHIYAMA
1976 Volume 24 Issue 1 Pages
10-15
Published: January 25, 1976
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Effect of zymosan, a typical reticuloendotherial stimulator, on hepatic drug-metabolizing enzymes was examined in mice. 1) When given in vivo, it depressed all the activities of aminopyrine N-demethylase, p-nitroanisole O-demethylase, and aniline hydroxylase. It was shown that the effect of zymosan on drug metabolism was exerted solely on microsomes and there was a marked decrease of cytochrome P-450 content in microsomes of zymosan-treated animals. 2) Aminopyrine N-demethylase activity was found to become minimum 24 hours after the administration of zymosan. On the other hand, phagocytic activity was enhanced at the same time when the maximum depression of the metabolism of aminopyrine was observed.
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SHOJI KOJIMA, MORIO KIYOZUMI, KAZUHIRO SAITO
1976 Volume 24 Issue 1 Pages
16-21
Published: January 25, 1976
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The excretion of cadmium through the bile and gastrointestinal mucosa after the intraperitoneal administration of cadmium chloride and the effect of the chelating agents such as ethylenediaminetetraacetic acid, citric acid, 2, 3-dimercapto-1-propanol, L-cysteine, D-cysteine, and DL-penicillamine on its excretion were studied in rats. The cumulative biliary excretion of cadmium in a 9 hr period was about 0.85% of the injected dose. Citric acid, D-cysteine, and DL-penicillamine increased the biliary excretion of cadmium. All of the chelating agents used scarcely affected the excretion of cadmium through the gastrointestinal mucosa. Moreover, chemical characteristics of cadmium complex in the bile were investigated by the chromatography on Sephadex G-75 of the bile from the rats receiving cadmium chloride. The results showed that cadmium was bound to several bile components with different molecular weights, and that cadmium in the bile of the rats administered cadmium chloride with the chelating agents such as citric acid, D-cysteine, and DL-penicillamine was largely bound to the substances with a low molecular weight.
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MASUMI SAKANE, HARUO KANAZAWA, AKIRA OHARA
1976 Volume 24 Issue 1 Pages
22-25
Published: January 25, 1976
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1) The present research has been planed to clarify the states of tryptophan residues in papain by means of N-bromosuccinimide (NBS) oxidation and photooxidation. 2) Only a tryptophan residue was exclusively modified by NBS oxidation with the loss of enzyme activity. 3) This residue was not affected by methylene blue-sensitized photooxidation. 4) Two of five tryptophan residues were not affected by NBS oxidation and photooxidation. 5) The first NBS-oxidizable tryptophan residue is considered to exist in or nearby the active site of papain. 6) The second and the third NBS-oxidizable tryptophan residues are considered to be identical with the photooxidizable residues. 7) The state of tryptophan residues of papain was illustrated schematically.
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TADAMASA HIRAYAMA, MASAHIRO KAMADA, HIDEAKI TSURUMI, MASATAKA MIMURA
1976 Volume 24 Issue 1 Pages
26-35
Published: January 25, 1976
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The action of anhydrous hydrogen chloride and bromide on sodium cyanoacetylcyanamides (II) and N-cyano-cyanoacetamidines (IV) was shown to undergo cyclization to give exclusively corresponding 2-halogenopyrimidines (VI, XV), whereas the hydrogen iodide treatment of II caused no cyclization and that of IV gave an unexpected 6-amino-4-iodopyrimidine (XVI). The reaction of II with alcoholic hydrogen chloride afforded 2, 6-dialkoxy-4-hydroxypyrimidines (VIII) via N-cyanoacetyl-O-alkylisoureas (VII). The intermediates (VII) were independently cyclized in water with heating to give 2-alkoxy-6-amino-4-hydroxypyrimidines (IX).
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HIDEO FUKUDA, TAKAO HAYAKAWA, JIRO KAWAMURA, YOSHIO AIZAWA
1976 Volume 24 Issue 1 Pages
36-45
Published: January 25, 1976
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In order to elucidate the role of some amino acid residues in bovine neurophysin II (NP-II) for its binding ability for oxytocin and vasopressin, NP-II has been photooxidized in the presence of rose bengal and oxygen, and the relationships between the loss of hormonesbinding ability of modified protein and the destruction of photosusceptible amino acids were examined. Photooxidation of NP-II causes rapid oxidation of single methionine residue to corresponding sulphoxide followed by a slow destruction of single tyrosine residue. More prolonged irradiation causes also slight decomposition of cystine residues. The hormonesbinding ability of NP-II is almost completely retained even when the methionine residue was completely photooxidized, but is gradually decreased with the progress of the photodegradation of the tyrosine residue. The decrease in binding ability of the photooxidized protein proceeds almost identically for oxytocin and [8-arginine] vasopressin as the ligand. The binding ability is decreased to about 70% of the original when 80% of tyrosine were degraded and to about 30% of the original when the tyrosine was completely photooxidized and about 6% of cystine residues were degraded. The influence of the destruction of tyrosine residue for the loss of hormones-binding ability of protein seemed to be amplified by the subsequent photooxidation of cystine residues since there is no direct correlation between the photodestruction of cystine residues and the decrease in the binding ability. The pH binding profiles of photooxidized NP-II are found to be essentially identical with those of native protein, indicating the non-essential role of phenolic hydroxyl group of tyrosine residue of NP-II in hormones-binding process. O-Acetylation of the tyrosine residue of NP-II with N-acetylimidazole gives no significant effect on the binding ability for oxytocin or [8-arginine] vasopressin. These findings suggest that the single methionine residue of NP-II has no contribution to the binding process, while the single tyrosine residue, particularly its aromatic ring, of NP-II may participate with the binding process of the protein to both oxytocin and vasopressin with similar contribution.
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MITSUO NAKAGAWA, YOICHI KAWASHIMA, MITSURU UCHIYAMA
1976 Volume 24 Issue 1 Pages
46-51
Published: January 25, 1976
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The chain elongation of labeled palmityl-CoA by rat liver microsomes was studied by radio-gas liquid chromatography after the incubation of the acid in a medium containing malonyl-CoA, β-mercaptoethanol, reduced nicotinamide adenine dinucleotide (NADH), reduced nicotinamide adenine dinucleotide phosphate (NADPH), KCN and sucrose under anaerobic conditions. The activity of chain elongation of palmityl-CoA to stearic acid was increased by refeeding starved rats. The activity in liver microsomes of refed rats was approximately twice greater than that of normal rats. Lipid phosphorus contents in liver microsomes of normal (15.4±0.8μg P/mg protein) and refed rats (15.3±1.6μg P/mg protein) were unchanged. However, the reaction was stimulated by the addition of sonicated dispersion of phosphatidylcholine. The stimulatory effect of the dispersion was more remarkable for refed rats than for normal ones. On the other hand, the chain elongation activity of palmityl-CoA was decreased by acetone extraction or phospholipase C treatment of liver microsomes of refed rats. The decreased activity was partially or completely restored by the addition of sonicated dispersion of phosphatidylcholine. These results suggest that phospholipids may play an important role for chain elongation reaction of fatty acids in liver microsomes of rats.
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KAZUO ITO, MITSUMASA HARUNA, YOKI JINNO, HIROSHI FURUKAWA
1976 Volume 24 Issue 1 Pages
52-55
Published: January 25, 1976
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Crystamidine is a new Erythrina alkaloid, which has been isolated from Erythrina crysta-galli LINN. (Japanese name : Hosoba Deiko) (Leguminosae) along with six known bases, N-nororientaline (I), erybidine (II), erythraline (III), erythrinine (IV), erysodine (VI) and erysotrine (VII). Chemical and spectral investigations of crystamidine showed that it should have the stereostructure (VIII).
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ISAO KITAGAWA, HIROTAKA SHIBUYA, HIDEKAZU TAKENO, TAKAO NISHINO, ITIRO ...
1976 Volume 24 Issue 1 Pages
56-60
Published: January 25, 1976
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As a continuation of the previous work, the structures of four minor products, which were obtained by HCOOH-acetone (1 : 2) treatment of 5α, 6α-epoxy-eudesman-8β, 12-olide (1) along with previously elucidated four products : A (2), B (3), C (4), and D (5), have been elucidated as E (6), F (7), G (8), and H (9). It has become clear that 1 was converted to five eremophilanolides (A, B, D, F, and H) via a biogenetic-type 1, 2-shift of the angular methyl at C-10, and the structure requirement for the ready conversion has been discussed. In addition, preparative liquid chromatography was undertaken to clarify the accurate product composition of the above acid treatment.
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JUTARO OKADA, TOSHIYUKI ESAKI, KUNIMI FUJIEDA
1976 Volume 24 Issue 1 Pages
61-71
Published: January 25, 1976
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The
13C nuclear magnetic resonance spectra of thirty 4-substituted antipyrine derivatives were examined to obtain the following conclusions : (i) the shielding constants of antipyrine were estimated using the CNDO/2 method ; the signal assignment using the shielding constants was consistent with that based on the experiments ; (ii) the
13C-
2H coupling constants of antipyrine were estimated using the CNDO/2 method ; the calculated values are in good agreement with those observed ; (iii) the additive equation on the chemical shifts of the sp
3-hybridized carbon was estimated ; the so-called steric effects were observed as a result of this analysis ; and (iv) the Hansch analyses were carried out regarding C-4 of the antipyrine derivatives as the so-called biological active center ; the agreement between the values estimated by the Hansch equation and those observed was fairly good for the analgesic activities.
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MAMORU SUGIURA, MASAKAZU ISOBE
1976 Volume 24 Issue 1 Pages
72-78
Published: January 25, 1976
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The lipase from Chromobacterium was adsorbed on glass beads which was coated with olive oil, liquid paraffin or silicone oil. These adsorption was treated in the Lineweaver-Burk's plot and characters of the adsorption were similar each other regardless of their chemical structure of hydrophobic materials. On the other hand, esterase from porcine liver was not adsorbed on hydrophobic glass beads. The interaction between the lipase and hydrophobic surface conformed to the Langmuir's adsorption isotherm with a dissociation constant K=1.4×10
-7M. At saturation of the surface with the lipase each protein molecule occupies an average area of 4500 A
2 per molecule. The lipase adsorbed on hydrophobic surface did not inactivated but activated about 3-fold. It was elucidated that the hydrophobic bond play a major role in the adsorption of the lipase on substrate or hydrophobic surface.
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YOSHIO TAKEDA, HIROYUKI INOUYE
1976 Volume 24 Issue 1 Pages
79-84
Published: January 25, 1976
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Administration experiments of (7, 8-
3H
2)-7-deoxyloganic acid (5) into Lonicera morrowii, Cornus officinalis and Gentiana thunbergii plants revealed that the C-8 proton of (7, 8-
3H
2)-5 was retained in loganin (2), secologanin (3) and morroniside (1), respectively.
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JUN ADACHI, KEIICHI NOMURA, KEMMOTSU MITSUHASHI
1976 Volume 24 Issue 1 Pages
85-91
Published: January 25, 1976
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1, 2, 3, 4, 5, 6-Hexahydro-1, 5-methanopyrido [3, 2-c] azocine and 1, 2, 3, 4, 5, 6-hexahydro-2, 6-methanopyrido [2, 3-d] azocine derivatives were synthesized by condensation reactions of acyl derivatives of 2-azabicyclo [3.3.1] nonan-7-one (XIa) with β-aminoacrolein. The key compound (XIa) was obtained by lithium aluminum hydride reduction and the subsequent acid hydrolysis of 3-methoxy-5-oxo-3-cyclohexene-1-acetamide (IXa), which was prepared starting from 3, 5-dihydroxyphenylacetic acid (IV). Mass spectra of the above pyridine derivatives were briefly described, too.
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YAEKO KONDA, YOKO SUZUKI, SATOSHI OMURA, MASAYUKI ONDA
1976 Volume 24 Issue 1 Pages
92-96
Published: January 25, 1976
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The alkaloid (1) obtained from Thermoactinomyces strain TM-64 is proven to be N-3'-β-indolylethyl-2-α-aminoethylthiazole-4-carboxamide on the basis of its chemical reactions and the physico-chemical method.
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CHINGTAN CHEN, KEIJIRO SAMEJIMA, ZENZO TAMURA
1976 Volume 24 Issue 1 Pages
97-101
Published: January 25, 1976
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A gas chromatographic determination method of 5-chloro-7-iodo-8-quinolinol (CF), its glucuronide (CF-G) and sulfate (CF-S) in serum, urine and milk was developed. 5, 7-Dichloro-8-quinolinol and/or 5-chloro-7-bromo-8-quinolinol, and their glucuronides and sulfates were added to the sample as the internal standards. Successive extractions with pyridine-benzene (1 : 9) without treatment, after hydrolysis with β-glucuronidase and that with 1 N HCl at 40°, gave the fractions of free quinolinols, derived from the unconjugated, the glucuronides and sulfates, respectively. The free quinolinols were acetylated and determined by gas chromatography. The present method was a demonstration of an effective use of structurally similar internal standards for determination of a glucuronide and sulfate.
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ICHIRO ISAKA, KOHZI NAKANO, TERUYA KASHIWAGI, AKIO KODA, HIROSHI HORIG ...
1976 Volume 24 Issue 1 Pages
102-107
Published: January 25, 1976
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Several lactol esters of D-α-aminobenzylpenicillin hydrochloride (Va-e) were synthesized from the corresponding lactol esters of benzylpenicillin (IIa-e) or from D-α-aminobenzylpenicillin (ampicillin). The lactol esters IIa-e were prepared with potassium benzylpenicillinate (I) and certain halides of lactols. Among them, two isomers of 2 (5H)-furanone-5-yl benzylpenicillinate (IIb) could be easily separated from the mixture of the stereoisomers due to C
5' position of the lactol moiety. We found that all of these lactol esters of ampicillin hydrochloride (Va-e) showed higher blood concentrations of ampicillin after oral administration to rats than that of ampicillin itself. Particularly Va and Ve were much superior.
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HIKARU OKABE, KAZUHIDE INOUE, TATSUO YAMAUCHI
1976 Volume 24 Issue 1 Pages
108-113
Published: January 25, 1976
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Eight cardiac glycosides, 3-O-α-L-rhamnopyranosides and 3-O-β-D-glucopyranosyl-(1→4)-α-L-rhamnopyranosides of corotoxigenin, mallogenin, coroglaucigenin and panogenin, were isolated from the seeds of Mallotus japonicus MUELL. ARG. (Euphorbiaceae).
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FUMIHIDE SAKAI, HIROAKI OHKUMA, HIDEO KOSHIYAMA, TAKAYUKI NAITO, HIROS ...
1976 Volume 24 Issue 1 Pages
114-120
Published: January 25, 1976
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The structure of breynogenin (C
22H
26O
9S), an aglycone of breynin A, was established as III on the basis of chemical and spectral investigations. The structure of isobreynogenin (C
22H
26O
9S), a secondary degradation product from breynin A, was determined as IV. Partial structure for breynin A has been presumed.
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ISAO KITAGAWA, MASAYUKI YOSHIKAWA, ITIRO YOSIOKA
1976 Volume 24 Issue 1 Pages
121-129
Published: January 25, 1976
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Soyasaponin I (major), II and III, all of which possess soyasapogenol B (2) as the common aglycone, have been isolated from the MeOH extractive of soybean (Glycine max MERRILL, Leguminosae). On the basis of chemical and physicochemical evidence, the structure of soyasaponin I has been elucidated to be 3-O-[α-L-rhamnopyranosyl (1→2)-β-D-galactopyranosyl (1→2)-β-D-glucuronopyranosyl]-soyasapogenol B (7) and the structures of soyasaponin II and III to be 3-O-[α-L-rhamnopyranosyl (1→2)-α-L-arabinopyranosyl (1→2)-β-D-glucuronopyranosyl]-soyasapogenol B (8) and 3-O-[β-D-galactopyranosyl (1→2)-β-D-glucuronopyranosyl]-soyasapogenol B (9), respectively.
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RENZO DOHMORI, SHIZUO KADOYA, ISAO TAKAMURA, NORIO SUZUKI
1976 Volume 24 Issue 1 Pages
130-135
Published: January 25, 1976
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By using 6-aminobenzothiazoles as starting meterial, a series of 2-substituted 6-ethyl-6, 9-dihydro-9-oxothiazolo [5, 4-f] quinoline-8-carboxylic acids has been prepared through successive steps of, e.g. condensation with diethyl ethoxymethylenemalonate, Gould-Jacobs reaction, N-alkylation and hydrolysis. These compounds were evaluated for antibacterial activities in vitro. The 2-chloro derivative (10d) showed nearly the same activity with nalidixic acid.
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SHIZUO KADOYA, ISAO TAKAMURA, NORIO SUZUKI, RENZO DOHMORI
1976 Volume 24 Issue 1 Pages
136-146
Published: January 25, 1976
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In order to search for new antimicrobial agents, a number of 2-substituted 6-ethyl-6, 9-dihydro-9-oxothiazolo [5, 4-f] quinoline-8-carboxylic acids were prepared. Nucleophilic reactions of the 2-methylsulfonyl derivative (6 or 13) gave the 2-alkoxy (12), 2-cyano (14), 2-amino (15 and 19) and other derivatives. By using the 2-cyano compound (3 or 14), various derivatives were also prepared, e.g., the 2-amidine (24h), 2-imido-ether (27), 2-carbamoyl (26 and 30) and other derivatives. Formation of the 9-ethoxy compound (33) by ethylation of the 8-decarboxylated compound (34) was also described. These compounds obtained were tested for their antimicrobial activities in vitro. The 2-cyano (14), 2-carbamoyl (26), 2-diethylaminoethylcarbamoyl (30f) and some other derivatives showed the stronger activities than nalidixic acid. The most active compound, 30f, exhibited the activities against Escherichia coli resistant to nalidixic acid, but had no activity against Ps. aeruginosa.
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SHIZUO KADOYA, NORIO SUZUKI, ISAO TAKAMURA, RENZO DOHMORI
1976 Volume 24 Issue 1 Pages
147-155
Published: January 25, 1976
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For the search of the more active antimicrobial compounds than the 2, 6-disubstituted derivatives, 3, 6-disubstituted 2, 3, 6, 9-tetrahydro-2, 9-dioxothiazolo [5, 4-f] quinoline-8-carboxylic acid (1, 3, 7, 8, 11, 20, 21, and 22) were synthesized from the 2-oxo-6-substituted thiazolo [5, 4-f] quinoline derivatives (2, 17, or 18). Thermal rearrangement of the 2-methylthio derivative (23) gave the 2-thioxo-3-methyl derivative (24), which was converted into the 2-oxo-3-methyl derivative (26) by reaction with mercuric acetate. The 2-ethoxy derivative (27) was also thermally rearranged to give the 2-oxo-3-ethyl derivative (8b). The 3, 6-disubstituted compounds obtained in this work showed the stronger activities against gram-negative and gram-positive bacteria in vitro than nalidixic acid and the 2, 6-disubstituted derivatives prepared in the previous work. 6-Ethyl-2, 3, 6, 9-tetrahydro-3-methyl-9-oxothiazolo [5, 4-f] quinoline-8-carboxylic acid (8a) exhibited the strongest activities among these compounds against many gram-negative bacteria including E. coli resistant to nalidixic acid and Ps. aeruginosa, and against some gram-positive bacteria.
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KENJI INAGAKI, YOSHINORI KIDANI, HISASHI KOIKE
1976 Volume 24 Issue 1 Pages
156-159
Published: January 25, 1976
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The acid dissociation constant of 1-phenazinethiol and its metal chelate formation constants have been determined spectrophotometrically in a 50% (v/v) ethanol at 25±1°. Metal chelates of 1-phenazinethiol were synthesized, and the salient feature of infrared (IR) spectra of these chelates were discussed. Considering from the formation constant of zinc chelate and its IR spectrum, it may be suggested that zinc-sulfur linkage of the zinc chelate has covalent character.
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MASAYOSI YAMAGUCHI, TAKEO YAMAMOTO
1976 Volume 24 Issue 1 Pages
159-161
Published: January 25, 1976
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The effect of thyrocalcitonin (TCT) on the calcium content of liver slices has been studied. At 30 min incubation period, TCT significantly (p<0.01) increased the accumulation of calcium in the concentration range from 0.1 to 8.0 mU/ml with half-maximal concentration occurring at about 0.1 mU/ml. During the 60 min incubation period, the effect of TCT on the liver calcium accumulation was additively enhanced. On the other hand, the radiocalcium (
45CaCl
3) efflux in the absence of the hormone increased linearly during the incubation period. The radiocalcium efflux in the presence of the hormone increased later with time than that in the absence of the hormone, and the inhibition of efflux was 25% of the control (p<0.01). These data suggest that TCT increased calcium accumulation in the liver cells by inhibiting the efflux of calcium.
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TOSHIO NAMBARA, MUNETAKA NOKUBO
1976 Volume 24 Issue 1 Pages
162-165
Published: January 25, 1976
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As a series of the metabolic studies on the steroidal lipid-shifting drugs biotransformation of 16α-chloroestrone with the rat liver preparations has been investigated. The substrate was reduced to the 17β-hydroxyl derivative, when incubated with microsomes, but not with the 105000×g supernatant. In contrast, estrone was converted into estradiol with either of these enzyme preparations. The yield of 16α-chloroestradiol formed from 16α-chloroestrone by incubation with microsomes decreased with an increasing amount of added estrone indicating the occurrence of competitive inhibition. The properties of 17β-hydroxysteroid dehydrogenase involving 16α-chloroestrone have been described.
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KATSUHIDE MATOBA, TAKASHI MAEDA, KEIKO NAGASE, TAKAO YAMAZAKI
1976 Volume 24 Issue 1 Pages
165-168
Published: January 25, 1976
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With Grignard reagent, five-membered vinylogous esters gave 1, 2-addition products in a similar fashion to the cases for six-membered vinylogous esters. On the other hand, the six-membered vinylogous ester substituted with t-butyl group at the α-position of carbonyl function also gave only 1, 2-addition product. However the five-membered vinylogous ester substituted with hydroxy group at the α-position of methoxy group gave 1, 2-addition product and 1, 4-addition products. In these Grignard reactions, the catalytic effect of cuprous chloride was scarcely observed.
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HIDEO KOSHIYAMA, MASAMI HATORI, HIROAKI OHKUMA, FUMIHIDE SAKAI, HIDEYO ...
1976 Volume 24 Issue 1 Pages
169-172
Published: January 25, 1976
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Breynins are new sulfur-containing glycosides extracted from Breynia officinalis HEMSL (Family Euphorbiaceae). Two major components, breynins A (C
40H
56O
23S) and B (C
40H
56O
24S), were isolated and characterized. Breynins A and B showed significant hypocholesterolemic activity in rats at a daily dose of 0.005 mg/kg and 0.025 mg/kg, respectively.
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TAKAO MURAKAMI, KAZUMI AOYAMA, NOBUTOSHI TANAKA, CHIUMING CHEN
1976 Volume 24 Issue 1 Pages
173-175
Published: January 25, 1976
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Aus den oberirdischen Teilen von Pteris wallichiana AGARDH. wurde ein neues Indan-1-on-Derivat, Isopterosid C isoliert und als 2 (S), 3 (S)-3-Hydroxy-2, 4, 6-trimethyl-5-hydroxyathyl-indan-1-on-3-O-β-D-Glukosid (I) identifiziert.
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TAKUO KOSUGE, MASAMI YOKOTA
1976 Volume 24 Issue 1 Pages
176-178
Published: January 25, 1976
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The chemical structure of Higenamine, cardiac principle isolated from Aconitum japonicum THUMB., was identified as dl-demethyl coclaurine.
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TADASHI HONDA, TATSUSHI MURAE, TAKAHIKO TSUYUKI, TAKEYOSHI TAKAHASHI
1976 Volume 24 Issue 1 Pages
178-180
Published: January 25, 1976
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The structure of a new sapogenin, arjungenin, isolated from Terminalia arjuna was shown to be 2α, 3β, 19α, 23-tetrahydroxyolean-12-en-28-oic acid (I).
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