1-Benzylisochinolin bildet bei der Nitrierung 1-(4-Nitrobenzyl)-isochinolin bzw. 1-(4-Nitrobenzyl)-5-nitroisochinolin. 1-(4-Aminobenzyl)-isochinolin und 1-(4-Aminobenzyl)-5-aminoisochinolin sowie ihre Acetylderivate wurden neu hergestellt.

View full abstract

1-(o-Brombenzyl)-isochinolin wurde neu hergestellt. Das letztere wurde durch Erhitzen mit konz. Ammoniak auf 180∼190° unter Zusatz von Kupferbromur in 1-(o-Aminobenzyl)-isochinolin ubergefuhrt. Nebenbei entstanden 1-Benzylisochinolin und Dibenzoindolizin. 1-(o-Aminobenzyl)-isochinolin wurde uber sein 1, 2, 3, 4-Tetrahydrid nach der Pschorr'schen Synthese in das Noraporphin ubergefuhrt. Die Versuche, die durch die Pschorr'sche Synthese von 1-(o-Aminobenzyl)-isochinolin oder durch die Dehydrierung von Noraporphins das Dehydronoraporphin herzustellen, waren erfolglos.

View full abstract

4-Benzylquionline (V) was synthesized and from its nitration product, 4-(p-nitrobenzyl) quinoline (VI) was isolated. It was reduced to the amino compound and substituted with bromine atom via diazonium group. 4-(p-Bromobenzyl) quinoline (IX) thus obtained was identified with an authentic sample derived from 4-chloroquinoline (I) by the action of p-bromophenylacetonitrile (X).

View full abstract

Alkaloids were extracted from a sample of ephedra with ammoniacal ether, transferred into acid solution, and diluted to a certain volume. Aliquots of this test solution were reacted under heating with ninhydrin in the presence of ascorbic acid and pyridine. The intensity of the color developed was measured at the maximum absorbancy peak at 570 mμ. Alkaloid content was calculated from the regression line, subtracting the blank from the observed value. It was found that this method was hardly interfered by amino acids and ammonium salt present in ephedra, through a control test with the quantity of these acids and salt about several times as much as those contained in ephedra. For further check of the comparative accuracy and precision of this method of analysis, several sets of analytical data were evaluated. The results of estimation made according to this proposed procedure agreed well with those obtained by the method of Japanese Pharmacopoeia VI and their reproducibility was satisfactory.

View full abstract

The ring closure of 2-carboxy-3-indoleacetobenzylamide (V) was investigated. On dehydration with acetic anhydride and acetyl chloride the ring closure of the lactonetype occurred, furnishing 6-acetobenzylaminoindolo [2, 3-c] -2-pyrone (XIII) and 1, 3-dioxo-2-benzyl-1, 2, 3, 4-tetrahydro-β-carboline (XVII) with polyphosphoric acid in which the ring closure of the imide-type occurred instead of the lactone-type.

View full abstract

4-Hydroxyaminochinolin-N-oxyd wurde durch Einwirkung von Hydroxylamin auf 4-Chlorchinolin-N-oxyd neu hergestellt. Es war mit der bisher als 4, 4'-Hydrazochinolin-N, N'-dioxyd angesehene Verbindung identisch. Die fruher als 4, 4'-Hydrazochinolin-N, N'-dioxyd angesehene Verbindung muss man also als das 4-Hydroxyaminochinolin-N-oxyd berichtigen. 2-Chlor-4-aminochinolin wurde durch Einwirkung von Phosphoroxychlorid auf 4-Aminochinolin-N-oxyd oder auf 4-Hydroxyaminochinolin-N-oxyd hergestellt.

View full abstract

Chinaldin-N-oxyd gibt beim Behandeln mit Benzoylnitrat in Chloroform-Losung das 3-Nitrochinaldin-N-oxyd und das 2-Benzoyloxymethylchinolin mit einer Ausbeute von 20.6% bzw. 30.3%. Vermehrt man die Menge des Benzoylnitrates bei dieser Reaktion ist die Ausbeute beider Verbindungen geringer und ausserdem wird ein gelbbraunes Kristall vom Schmp. 249∼250° (Zers.) und von der Zusammensetzung C₂₀H₁₀O₆N₆ erhalten. Das letztere entsteht auch, wenn man das 3-Nitrochinaldin-N-oxyd mit Benzoylnitrat analogerweise behandelt. Fur die Konstitution des letzteren haben die Verfasser eine Glyoximsuperoxyd-Formel (E) vorgeschlagen.

View full abstract

3-Hydroxy-N-methyl-6-aza-des-N-morphinan was synthesized in accordance with the methods described earlier but the compound failed to show any analgesic activity. However, it had antitussive action somewhat weaker than that of codeine.

View full abstract

1. Pseudo-dihydrothiamine was found to possess hydroxyl and imino groups from the infrared absorption spectrum. 2. Normal-, iso-, and pseudo-dihydrothiamines give the same benzoyl-pseudo-dihydrothiamine. 3. It was concluded from foregoing results that pseudo-dihydrothiamine possessed a structure entirely different from that of normal- and iso-dihydrothiamine.

View full abstract

The relationship between the weight of target organs (ovary and uterus) and the uptake of radiophosphorus under the influence of gonadotropin was examined and the response was expressed as the counts per organ reduced by the analysis of covariance with the organ weight. Periodical change of radioactivity of the target organs was traced after the administration of radiophosphorus. The phosphorus-accumulating activity of the target organs after the administration of gonadotropin was studied and the maxima of those of ovaries and uterus were found respectively at the 72nd and 96th hour.

View full abstract

The ratio RNA-P/DNA-P was compared between the gonadotropin-treated group and the control, and the former showed a low ratio, suggesting a great mitotic activity while the latter showed a high ratio or low activity. Progesterone was found to be a hormone which accelerated the accumulation of the phosphorus at the estrogen-pretreated uterus. The radioisotope technique was applied to Aschheim-Zondek test and could shorten the assay period with a level of significance.

View full abstract

A new synthesis of dl-threo-2-benzamido-1-p-nitrophenyl-1, 3-propanediol from trans-p-nitrocinnamyl alcohol was described and the reaction mechanisms involved in the synthesis were discussed in connection with earlier conclusions. Stereospecificity in the displacement of C-3-bromine of dl-threo-2-amino-3-bromo-3-p-nitrophenylpropyl benzoate system in a dry condition was examined, hereby special effect of NO₂ radical on benzene ring to the displacement was presumed.

View full abstract

Isolation and chemical studies were carried out on an antibiotic which was produced by a new streptomyces, Streptomyces humidus nov. sp. From the physical, chemical, and microbiological properties of this antibiotic in crude state, it was found that this antibiotic belonged to the so-called streptomycin-group antibiotics, but differed from streptomycin, mannosidostreptomycin, and hydroxystreptomycin, which are produced directly by streptomycetes. This antibiotic was finally isolated as a pure crystalline sulfate. The physicochemical and microbiological properties of this sulfate and physicochemical properties of its degradation products showed that this sulfate was nothing but dihydrostreptomycin sulfate.

View full abstract

Durch Nitrierung von 3-Oxypyridin wurde das 2-Nitro-3-oxypyridin hergestellt, das beim Behandeln mit PCl₅ bzw. PBr₃ 2-Chlor-3-oxypyridin bzw. 2-Brom-3-oxypyridin liefert. 2-Amino-3-oxypyridin-Chlorhydrat ergibt durch die Acetylierung das 1-Acetyl-2-acetimido-3-acetoxypyridin, das durch Hydrolyse uber 2-Acetamido-3-acetoxypyridin das 2-Acetamido-3-oxypyridin liefert. Aus dem letzteren wurde 2-Methyloxazolo [4, 5-b]-pyridin und aus 2-Amino-3-oxypyridin-Chlorhydrat 2-Mercapto-oxazolo [4, 5-b] pyridin hergestellt.

View full abstract

From the analysis of the relation between pH and oxidation-reduction potential of artificial iron springs, the following facts were revealed. 1) In natural, strongly acidic vitriol spring, ferric ion exists mainly in the form of a complex cation, FeSO⁺₄ with sulfate ion, and its potential is given by equation (23). 2) In natural, weakly acidic vitriol spring, ferric ion forms FeSO⁺₄, FeOH²⁺, and Fe (OH)⁺₂, and its potential is given by equation (32). 3) In natural iron spring, much more weakly acidic than the above two cases, such as iron bicarbonated or iron carbondioxated springs, ferric ion deposits mainly as Fe (OH)₃, and its potential is given by equation (26). Ferrous ion in natural strongly acidic vitriol springs is easily oxidized by air to ferric sulfate complex cation, the oxidation velocity of which is more rapid than that of the artificial spring. Based on the test of artificial springs, it was assumed that a trace of vanadium, platinum, copper, and the like may catalyze the oxidation of ferrous ion by air in natural acidic vitriol springs.

View full abstract

The ninhydrin reagent for use in the quantitative determination of amino acids separated by paper chromatography was reexamined and modified, and the conditions under which the reagent could be used most advantageously were determined. The potency of the ascorbic acid contained in the reagent was stabilized by the use of 2% aqueous solution of metaphosphoric acid, and the blank test value and the range of variation in the determined value were minimized. This modified method surpasses the original in that it is less expensive, less sensitive to ammonia, and easier to use, than the latter.

View full abstract

Methylation of damnacanthal with diazomethane gave a methyl ketone derivative, while methylation with dimethyl sulfate and anhydrous potassium carbonate gave a monomethy ether and munjistin dimethyl ether (m.p. 263∼265°), and methylation with methyl iodide and silver oxide gave a trimethyl ether. The infrared absorption spectra of these methyl derivatives and other derivatives of damnacanthal were measured.

View full abstract

By the extraction of buds of Rhododendron linearifolium SIEB. ET ZUCC. VAR. macrosepalum MAKINO, a presence of a viscous matter was discovered, the properties of which were very similar to those of bird lime in Japanese market. By its saponification, ursolic acid, melissyl alcohol, motiol, and motic acid were separated. The latter two were proved to be new triterpenoids with following constants : Motiol, C₃₀H₅₀O, m.p. 217°, [α]²⁴_D -27.4. Motic acid, C₃₀H₅₀O₃, m.p. 283∼284°, [α]¹²_D-73.40.

View full abstract

Some considerations were made on the steric configuration of 3-hydroxy-9-aza-des-N-morphinan synthesized previously. It was thereby established that the octahydroquinoline formed during the course of its synthesis has a trans-configuration and that its cyclized product and demethylated, objective compound have the same steric configuration as that of morphine.

View full abstract

1) It was shown that Sepedonium ampullosporum DAMON produces rugulosin, skyrin, and chrysophanol. 2) Skyrin and emodin were found to be produced by Penicilliopsis clavariaeformis SOLMS-LAUBACH along with penicilliopsin. 3) On oxidation with selenium dioxide, penicilliopsin was directly converted into skyrin.

View full abstract

The identity of flavomycelin of Mycelia sterilia and luteoskyrin of Penicillium islandicum SOPP was established by the comparison of their physical and chemical properties.

View full abstract