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Yoshihisa Mizuno, Morio Ikehara, Fumiyoshi Ishikawa, Hiroshi Ikehara
1962 Volume 10 Issue 9 Pages
761-766
Published: September 25, 1962
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5-and 6-Nitrobenzimidazole ribofuranosides were synthesized from chloromercury salt of 5 (6)-nitrobenzimidazole and 2, 3, 5-tri-O-benzoyl-D-ribofuranosyl chloride in 15.6% and 24.2% yield respectively. The structure of both compounds was elucidated physicochemically. 4-Nitrobenzimidazole ribofuranoside was also synthesized by an analogous reaction.
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Morio Ikehara, Tohru Ueda, Kazuyoshi Ikeda
1962 Volume 10 Issue 9 Pages
767-771
Published: September 25, 1962
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Uridine was converted to 2', 3'-O-isopropylidene-5'-O-benzoyluridine and derived to 2', 3'-O-isopropylidene-4-methylthiouridine by successive thiolation and methylation. The latter compound was reacted with either CH
3NH
2 or (CH
3)NH
2 to produce 2', 3'-Oisopropylidene-N-methyl-or N, N-dimethylcytidine respectively. N-Methyl-and N, Ndimethylcytidine 5'-phosphate were synthesized by the poly-phosphoric acid method followed by the acidic removal of isopropylidene groups.
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Yuriko Kato
1962 Volume 10 Issue 9 Pages
771-788
Published: September 25, 1962
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Physical constants, such as surface tension, solubilization of pigments, polaography, refractive index, and viscosity, were measured of aqueous solution of 14 kinds of glycols of different number of carbon atoms, from propanediol to dodecanediol.
Glycols with hydroxyls on either terminal ends or in 1, 2-positions showed a break point in the foregoing physical constants and were considered to form a micelle-like structure.
Glycols with one hydroxyl at a terminal end and the other in a median position also forms a micelle-like structure but those having both hydroxyls in median positions and none at the terminal position do not form such a structure.
The concentration of glycols at which they form a micelle-like structure decreases with increasing number of carbon atoms and the concentration of dodecanediol becomes approximately equal to the critical micelle concentration of nonionic surfactant.
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Tohru Ueda
1962 Volume 10 Issue 9 Pages
788-791
Published: September 25, 1962
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The reaction of 5-bromo-2', 3'-isopropylideneuridine and dimethylamine gave 5-dimethylamina derivative and this was phaspharylated ta 5-dimethylaminauridine 5'-phosphate by polyphosphoric acid. 3-Methyluridine 5'-phosphate was also synthesized from 3-methyl-2', 3'-isopropylideneuridine by polyphosphoric acid.
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Kazuko Narahashi
1962 Volume 10 Issue 9 Pages
792-803
Published: September 25, 1962
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The structures of orixidine and orixidinine, both demethylation products of orixine, were discussed and their 2(1
H)-quinolone structures were established. It is assumed that orixidine and orixidinine should have structures (IV) and (XIII), respectively, while that of the isomeric transformation product of (XIV), iso-N-methylorixidinine, structure (XVI).
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Hiroshi Mitsuhashi, Ikuko Takemori, Yuzuru Shimizu, Taro Nomura, Emiko ...
1962 Volume 10 Issue 9 Pages
804-808
Published: September 25, 1962
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The whole plant of
Marsdenia tomentosa DECNE. was proved to contain a glycoside mixture which showed strong Keller-Kiliani reaction, suggesting the presence of 2-desoxy sugars. The suger part which was obtained by acid hydrolysis was found to be glucose and cymarose by the paper chromatography compared with the authentic specimens. The aglycones were presumed to be esters. Their alkaline hydrolysis afforded two kinds of crystals, tomentogenin, a new aglycone (m.p. 247-249°) and sarcostin (m.p. 150°/245-250°) and from acidic portions tiglic acid, isovaleric acid, and acetic acid were found.
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Hiroshi Mitsuhashi, Yuzuru Shimizu, Emiko Yamada, Ikuko Takemori, Taro ...
1962 Volume 10 Issue 9 Pages
808-811
Published: September 25, 1962
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The paper chromatographic separation of the polyhydroxy steroids in Asclepiadaceae plant was established. By this method, three aglycones were newly found in
Cynanchum caudatum. The deacylcynanchogenin was proved to be identical with lineolon from
Pachycarpus lineoratus.
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Hiroshi Mitsuhashi, Taro Nomura, Yuzuru Shimizu, Ikuko Takemori, Emiko ...
1962 Volume 10 Issue 9 Pages
811-817
Published: September 25, 1962
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The stems and leaves of
Metaplexis japonica MAKINO were proved to contain glycoside mixture. The glycoside showed the Keller-Kiliani reaction, suggesting the presence of 2-desoxy-sugar. The sugar portion of the glycoside was found to be D-cymarose and D-digitoxose by paper partition chromatography when compared with the authentic specimen. Five kinds of crystal, such as crystal No, 1, m. p.194-196°, crystal No.2, m. p.248/154°, crystal No.3, m. p.234-237°, crystal No.4, m. p.245°, and crystal No.5, m. p.264°, were isolated by adsorption chromatography using alurnina, and partition chromatography over Celite as a carrier. Crystal No.2 was identified to be sarcostin by the mixed melting point determination and the paper chromatography.
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Hiroshi Mitsuhashi, Teiko Hiroshige, Ikuko Takemori, Yuzuru Shimizu, T ...
1962 Volume 10 Issue 9 Pages
818-822
Published: September 25, 1962
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The stems and leaves of
Cynanchum caudatum MAX. were proved to contain a glycoside mixture. The sugar portion of the glycoside was found to be D-cymarose by paper partition chromatogoraphy comparing with an authentic specimen.
Six kinds of aglycone, such as deacylcynanchogenin, sarcostin, crystal, m. p.215-220°, and other 3 spots were found by paper partition chromatography. They were isolated by adsorption chromatography using alumina, and partition chromatography over Celite as a carrier.
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Harutada Negoro, Shogo Ueda, Toshihiko Hoshi
1962 Volume 10 Issue 9 Pages
823-827
Published: September 25, 1962
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Dissociation constants of the complex between pyrazine-or pyridine-monocarboxamide and Na-PAS in aqueous solution (K) were obtained at various temperatures (T) mthe absorption spectra measurment, then heats of complex formation ΔHc were evaluated from the correlation between log K and 1/T. Thus obtained, ΔHc value by the spectral method exceedingly differs from that thermal method considering the experimental error, so the discussion was made on this reason.
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Yukio Kameda, Katsuhiko Matsui, Yukio Kimura, Etsuko Toyoura, Eiji Tak ...
1962 Volume 10 Issue 9 Pages
827-830
Published: September 25, 1962
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The metabolic activities of 3 strains (KT-303, KT-304, and KT-305) of soil bacteria were tested on tryptophan and its benzoyl derivatives (Table I), and it was found that KT-303 and KT-305 metabolized benzoyl-DL-tryptophan to produce L-tryptophan and benzoyl-D-tryptophan respectively.
Two strains (KT-230 and KT-231) of soil bacteria had the activity to metabolize benzoyl derivatives of 2-aminohexanedioic acid and 2-aminooctanoic acids to yield L-2-aminohexanedioic acid, N-benzoyl-D-2-aminohexanedioic acid, L-2-aminooctanoic acid, and N-benzoyl-D-2-aminooctanoic acid respectively.
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Yukio Kameda, Tomoo Omori
1962 Volume 10 Issue 9 Pages
831-833
Published: September 25, 1962
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Acertain strain (KT-313) isolated from soil had the metabolic activity shown in Table I and could metabolize di-N
2, N
6-benzoyl-DL-lysine (I) and N
2-phenacyl-N
6-benzoyl-DL-lysine (II) to produce N
6-benzoyl-L-lysine (III), di-N
2, N
6-benzoyl-D-lysine (IV) and N
2-phenacyl-N
6-benzoyl-D-lysine (V), respectively. KT-313 seemingly belongs to the
Pseudomonas group. It is of interest that KT-313 hydrolyzed benzoyl (III B) and phenacyl (III P) derivatives of N
6-benzoyl-L-lysine (III), while KT-301 hydrolyzed (III B), but not (III P), and KT-311 hydrolyzed (III P), but not (III B).
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Tchan Gi Bak, Shigeaki Kuwano
1962 Volume 10 Issue 9 Pages
833-841
Published: September 25, 1962
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Gallic acid and
d-catechin inhibitions of glutamic and arginine decarboxylases of
Escherichia coli occur in both reversible and irreversible manners. Gallic acid competes with the substrate in glutamic decarboxylase and with pyridoxal phoshate in arginine decarboxylase, whereas the interactions of
d-catechin in both enzymes are of noncompetitive nature with respects to both substrates and pyridoxal phosphate. Gallicacid and
d-catechin combine with glutamic decarboxylase protein at different sites.
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Hiromu Mori, Vipichandra S. Gandhi, Erwin Schwenk
1962 Volume 10 Issue 9 Pages
842-851
Published: September 25, 1962
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Some 4, 4-dimethy1-2-hydroxy-Δ
1-3-one type steroids (diosphenols) were prepared as potential tumor growth inhibiting chemotherapeuticals modeled on the cancer inhibiting elatericin B. These substances were obtained from 4, 4-dimethyl-3-oxo steroids by selenium dioxide oxidation, by a method via the 2-bromo compound, by a method via the 2-oximino compound or by autoöxidation. The last two procedures were found to be the most suitable for the preparation of the desired substances.
The diosphenols we obtained were as follows: 2-hydroxylanosta-1, 8, 24-trien-3-one (VIa), 2-hydroxylanosta-1, 8-dien-3-one (VIb), 2-hydroxy-3-oxo-4, 4, 14α-trimethyl-Δ
1, 8-5α-choladienicacid (VId), 2, 17β-dihydroxy-4, 4-dimethylandrosta-1, 5-dien-3-one (XVIa), 2-hydroxy-4, 4-dimethyl-22α-spirosta-1, 5-diene-3-one (XVIc), 3-oxo-2, 12α-dihydroxy-4, 4-dimethyl-Δ
1, 5-choladienic acid (XXIa), 2-hydroxy-3, 12-dioxo-4, 4-dimethyl-Δ
1, 5-choladienic acid (XXVa), and 2-hydroxy-4, 4-dimethylergosta-1, 5, 7, 22-tetraen-3-one (XXVIII). 4-Hydroxy-3, 12-dioxo-Δ
4-cholenic acid (XXVII) was also prepared.
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Studies on the Utilization of Safrole as Medicinal Raw Material. XVII. Synthesis of 3-Methyl-9, 10-methylenedioxy-1, 2, 3, 3a, 4, 5, 11b, 11c-octahydro-7H-pyrrolo [3, 2, 1-de] phenanthridine
Kohzoh Okada
1962 Volume 10 Issue 9 Pages
852-856
Published: September 25, 1962
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A synthesis of 3-methyl-9, 10-methylenedioxy-1, 2, 3, 3a, 4, 5, 11b, 11c-octahydro-
7H-pyrrolo [3, 2, 1-
de] phenanthridine (XIV) having common hydropyrrolophenanthridine skeleton with several of the
Amaryllidaceae alkaloid such as lycorine, pulviine, caranine etc., was described. 2-(3, 4-Methylenedioxyphenyl)-5-methylcyclohexanone (VI) prepared from safrole was used as the starting material. This synthesis had recourse to the fact that the starting ketone underwent the Mannich reaction with formaldehyde and dimethylamine at its 6-position and not at 2-position to give 2-3, 4-methylenedioxyphenyl-5-methyl-6-dimethylaminomethylcyclohexanone (VII). This fact was evidenced by the ultraviolet absorption date showing the presence of an ethylene bond conjugated to the aromatic ring in the unsaturated lactam (IX) prepared from (VI) via the 2-oxo-cyclohexaneacetonitrile (VIII) by Campbell cyclization. Catalytic hydrogenation followed by lithium aluminium hydride reduction converted (VIII) into octahydroindole derivative (XIII) through the saturated lactam (XII). The ultimate base (XIV) was readily obtained from (XIII) by the conventional Pictet-Spengler method.
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Kyosuke Tsuda, Susumu Ikuma, Masaaki Kawamura, Ryuji Tachikawa, Yoshih ...
1962 Volume 10 Issue 9 Pages
856-865
Published: September 25, 1962
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Kyosuke Tsuda, Susumu Ikuma, Masaaki Kawamura, Ryuji Tachikawa, Tetsuo ...
1962 Volume 10 Issue 9 Pages
865-867
Published: September 25, 1962
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In der vorhergehenden Mitteilung hatten die Autoren darauf hingewiesen, daß es sich bei der Struktur der C
9-Base um 2-Amino-6-hydroxymethyl-8-chinazolinol (VIIb) handeln kann.
In dieser Arbeit berichten die Autoren über die Totalsynthese des C
9-Base-methyläthers (VIIa): Als Ausgangsmaterial diente den Autoren das leicht zugängliche 5-Methoxy- iso-phthaloylchlorid (I), über dessen Herstellung bereits von Calandra,
et al. berichtet worden ist. Durch Reduktion von (I) mittels Lithium-tri-tert-butoxyaluminiumhydrid in Diglyme wurde 5-Methoxy-iso-phthalaldehyd (II) und daraus wiederum durch Nitrierung sein 4-Nitroderivat (III) erhalten. Zur Bestimmung der Einführungsstelle der Nitrogruppe ließ sich das (III) durch Oxydation mittels Silberoxyd und darauffolgende Veresterung in den bekannten 5-Methoxy-4-nitro-iso-phthaloyl-dimethylester (VIIIb)überfuhren. Die Ferrosulfat-Reduktion von (III) ergab 4-Amino-5-methoxy-iso-phthalaldehyd (IV), der bei der partiellen Reduktion mittels Lithium-tri-
tert-buthoxyalumilliumhydrid in Diglyme unter geeigneten Bedingungen ein Gemisch von 2-Amino-5-hydroxymethyl-3-methoxybenzaldehyd (V) und 4-Amino-5-hydroxyrnethyl-3-methoxybenzaldehyd (VI) ergab. Diese beiden Aldehyde ließen sich durch Chromatographie mittels Aluminiunzoxyd trennen und in reiner Form gewinnen.(V) unterschied sich durch sein für die
o-Aminobenzaldehydgruppierung charakteristisches IR-Spektrum und gab bei der Cyclisation mit Guanidin das 2-Amino-6-hydroxymethyl-8-methoxychinazolin vom Schmp. 223-224°(VIIa).(VIIa) erwies sich nach allen Daten als identisch mit C
9-Base-methyläther.
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Kyosuke Tsuda, Susumu Ikuma, Masaaki Kawamura, Ryuji Tachikawa, Tetsuo ...
1962 Volume 10 Issue 9 Pages
868-870
Published: September 25, 1962
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Michihiro Yamada
1962 Volume 10 Issue 9 Pages
871-872
Published: September 25, 1962
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Treatment of 14-bromocodeinone, prepared from thebaine, with zinc-dust in glacial acetic acid gave codeinone, m. p.181-182°. Codeinone was quantitatively reduced to codeine with sodium borohydride.
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Katsuaki Matsui, Saburo Akagi, Fukutaro Ugai
1962 Volume 10 Issue 9 Pages
872-875
Published: September 25, 1962
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From the alkaloid-free fraction of opium, β-sitosteryl-D-glucoside and its monopalmitate, (+)-10-nonacosanol,
cyclo-laudenol and
cyclo-artenol were isolated.
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Kazuko Yamauchi, Tchan Gi Bak, Shigeaki Kuwano
1962 Volume 10 Issue 9 Pages
876-878
Published: September 25, 1962
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Previous studies from this laboratory have established that the alkaloid berberine inhibits two typical vitamin B
6-enzymes of bacterial origins, i. e. tyrosine decarboxylase of
Streptococcus faecalis and tryptophanase of
Escherichia coli. Evidence has also been reported to indicate that berberine inhibits these enzymes by competing with the coenzyme pyridoxal phosphate. It has further been shown that the alkaloid, once combined with the apoenzymes, causes slow and irreversible inactivation of the enzymes.
The present investigation was undertaken to examine if berberine behaves similarly toward pig heart glutamic-aspartic transaminase, a typical B
6-enzyme of mammalian tissues. The results obtained were, however, rather contrary to expectation; no inhibition by berberine could be observed in spite of many attempts. It appears, therefore, that the susceptibility of the mammalian
6 enzyme is significantly different from that of bacterial
6 enzymes for reasons to be elucidated in future.
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Mitsutaka Natsume
1962 Volume 10 Issue 9 Pages
879-883
Published: September 25, 1962
Released on J-STAGE: January 31, 2011
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Toshihiko Okamoto, Mitsutaka Natsume, Hiroshi Zenda, Susumu Kamata
1962 Volume 10 Issue 9 Pages
883-886
Published: September 25, 1962
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