Carbohydrate utilization and nitrogen requirement of Trichophyton gypseum were studied and differences in the nutritional physiology between the normal and pleomorphic forms of this fungus were demonstrated. The pleomorphic form showed better growth and more efficient assimilation on monosaccharides than the normal form. Dior polysaccharides generally failed to support appreciable growth of either form. The pleomorphic form grew far more readily on single amino acid than the normal form, and reproduced even on ammonium nitrogen to some extent which the normal form could not utilize at all.
The effect of synthetic fungicides and fatty acids on the respiration of normal and pleomorphic forms of Trichophyton gypseum was examined manometrically. Organic thiomercuric fungicides, cationic detergents, and undecylenic acid markedly inhibited the respiration in as low as 10-3 to 10-5 molar concentration. Close relationship was observed between their respiration- and growth-inhibiting effects. The pleomorphic form was much more sensitive to the action of these compounds than the normal form of this fungus. Every saturated fatty acid of even-numbered series from C2 to C16 stimulated the respiratory rate of this fungus in a certain range of concentrations, while higher members among them above C8 inhibited it in relatively higher concentration. The inhibitory action was stronger in the undissociated state than as anion of the same acid, and was the maximum with the C12 acid. This dermatophyte was more sensitive to the action of these acids than bacterial species examined.
The action of Trichomycin on the respiration and phosphorus metabolism of Trichophyton gypseum was examined. This antibiotic stimulated the respiratory rate of this fungus in a range of 0.1∼100γ/cc., while it inhibited the rate markedly over 100γ/cc. The inhibitory action of Trichomycin upon the incorporation of phosphate into the cells from the surrounding medium was demonstrated with the aid of 32P-labeled phosphate. Such an effect appeared from 0.1γ/cc.
Naphthoresorcinol picrate, 1 : 1 molecular compound, is recommended for the microdetermination of glucuronic acid. The new reagent is advantageous over the usual naphthoresorcinol in the stability on storage, both in crystalline and solution state, and it exhibits higher absorbancy and better reproducibility. The standard procedure was established. It has been found that the measurement of glucuronide with this reagent in the presence of glucuronic acid is possible by employing an alkaline bromine method instead of hypoiodide procedure described by Fishman, et al.
Extensive studies were made for the detection of terpene alcohols, aldehydes, ketones, and lactones by paper electrophoresis. The method is generally available for a rapid test of perfume products and it could be accomplished more rapidly than chromatography on paper by using a current of 500∼8, 000 V, reported previously. The higher the voltage, the sooner the results are obtained in electrophoresis, while a constant time was required in chromatography owing to the constant capillarity of the filter paper itself. One of many electrolytes applied, mercuric chloride, has shown the most satisfactory result and a formation of conjugated carbonyl groups with mercuric ion was presumed.
The position of bromine substituted by bromination of 1, 3-cyclohexanedione monoenolate with N-bromosuccinimide was investigated. 1, 3-Cyclohexanedione monoenolates, which have no or one aryl substituent in their 5-position, were found to be brominated with the N-bromosuccinimide at the 2-position.
The position of the substituted bromine in bromination of 1, 3-cyclohexanedione monoenolate with N-bromosuccinimide was investigated. 1, 3-Cyclohexanedione-3-monoenolates, which have two alkyl substituents at their 5-position, were found to be brominated at positions other than 2. From the data obtained in infrared spectra, the stereochemical situations of the bromo substitution were discussed. In this reaction dibromo compounds were obtained as by-products which were not found in a similar reaction for 1, 3-cyclohexanedione monoenolates having no or one aryl substituent at their 5-positions.
The position of substituted bromine in the product obtained by bromination with N-bromosuccinimide of 1, 3-cyclohexanedione 3-monoenolates having two alkyl substituents at the 5-position was established as 6, probably in axial conformation.
Two synthetic routes to a compound having the structure analogous to the A-ring of tetracycline, 2-phenylcarbamoyl-5, 5-dimethyl-6-(1-piperidyl)-1, 3-cyclohexanedione, were established. The desired compound was obtained by amination of 2-phenylcarbamoyl-5, 5-dimethyl-6-bromo-1, 3-cyclohexanedione with piperidine. The antibacterial properties of the final product are reported.
About sixty kinds of dibenzofuran derivatives having one or two substituents were synthesized, and relationship between kinds and positions of substituents and antibacterial action, especially against Mycobac. tuberc. A. T. C. C. No. 607, was discussed.
About forty kinds of dibenzothiophene, fluorene, and carbazole derivatives were synthesized and the relationship between chemical structure and antibacterial action, especially against Mycobac. tuberc. A. T. C. C. No. 607, was elucidated in comparison with these of dibenzofuran derivatives.
The relationship between the chemical structure and antibacterial activity observed in compounds related to dibenzofuran was conclusively elucidated. Some attempts were also made for studying the mode of action of these compounds.
Additional three metabolites of methylhexabital (MHB, 5-cyclohexenyl-3, 5-dimethylbarbituric acid) were isolated from the urine of rabbits receiving MHB and chemical structures of two of these compounds were established as 5-(3-oxo-1-cyclo-hexenyl)-5-methylbarbituric acid and β-5-(3-hydroxy-1-cyclohexenyl)-3, 5-dimethyl-barbituric acid. The main metabolites obtained to date were diastereoisomeric 3-OH-MHB[α-and β-5-(3-hydroxy-1-cyclohexenyl)-3, 5-dimethylbarbituric acid, in which α-form was considerably predominant]and 3-keto-MHB[5-(3-oxo-1-cyclohexenyl)-3, 5-dimethyl-barbituric acid].
The ester-type PAS-glucuronide was isolated from the urine of rabbit receiving PAS and the structure was established as methyl (4-acetamido-2-acetoxybenzoyl 2, 3, 4-tri-O-acetyl-β-D-glucopyranosid) uronate, which was synthesized. m-Aminophenyl glucuronide was isolated from the urine of rabbit. p-Aminosalicyluric acid, m-aminophenyl sulfate, and the ether-type PAS-glucuronide were detected in the urine by means of paper chromatography.
Both ether and ester glucuronides of salicylic acid were detected by paper chromatography in the urine of rabbits receiving salicylic acid. The ether glucuronide was isolated as methyl (o-methoxycarbonylphenyl 2, 3, 4-tri-O-acetyl-β-D-glucopyranosid) uronate and the structure was confirmed with the synthetic compound.
The pigment B, isolated from Penicillium islandicum SOPP, N. R. R. L. 1175, and also found in the mycelium of Endothia parasitica ANDERSON ET ANDERSON, was studied. The pigment B which was named oxyskyrin gave a molecular formula, C30H18O11, and yielded heptaacetate and heptabenzoate. On reductive cleavage with alkaline sodium dithionite, oxyskyrin was decomposed to give emodin and ω-hydroxyemodin. On oxidation with chromium trioxide, oxyskyrin heptaacetate was converted into skyric acid hexaacetate. Consequently, oxyskyrin was formulated as 2, 4, 5, 2', 4', 5'-hexahydroxy-7-methyl-7'-hydroxymethyl-bianthraquinone-(1, 1').
1, 4-Dibenzoylthiosemicarbazide (II) is converted by the action of alkali principally into 3-phenyl-5-mercapto-1, 2, 4-triazole (IV) and benzoic acid. The reaction route was studied by using 14C-tracer technique. It was thereby found that (II) affords 1-benzoyl-thiosemicarbazide (A) and benzoic acid in the first step and (A) further cyclizes to (IV), while a part of (A) decomposes into benzoic acid and ammonia. 1, 4-Dibenzoylsemicarbazide also behaves in analogous manner.
(1) ACh dose-response curve in the presence of various concentrations of antagonist was traced fully and it was suggested experimentaly that the curve moved parallel by the atropine-like action and its maximum response was depressed noncompetitively by the papaverine-like action. (2) It was made possible to discriminate precisely the atropine-like action as competitive antagonism to a low concentration of ACh 4×10-8g./cc. and the papaverinelike action as non-competitive antagonism to a high concentration of ACh (1.11×10-4g./cc.). (3) The potency ratios in relaxing the contraction due to the high concentration of ACh was almost the same as the ratios against BaCl2.
1) 4-Methyl-6-chloro-3-pyridazinol (IIIa) and 5-methyl-6-chloro-3-pyridazinol (IIIb) were obtained from 4-methyl-3, 6-dichloropyridazine (I) by refluxing with glacial acetic acid. 2) 4-Carboxy-6-chloro-3-pyridazinol (II) was formed from 4-methyl-3, 6-dichloropyridazine (I) and 4-methyl-6-chloro-3-pyridazinol (IIIa) by oxidation with potassium dichromate in conc. sulfuric acid and it was led to ester (VI), hydrazide (VII), and amide (VIII) derivatives. 3) 5-Carboxy-6-chloro-3-pyridazinol (IX) was also obtained by similar procedure from 5-methyl-6-chloro-3-pyridazinol (IIIb).
Nineteen kinds of amino acid contained in beet molasses from Hokkaido were quantitatively separated and analyzed by the new method in which ion exchanger and paper partition chromatography were applied, when the amino acids were mixed with sugars, proteins and other inorganic substances.
It was proved that formate labeled with 14C is incorporated into γ-methyl and Nmethyl groups in l-ephedrine molecule in Ephedra distachya. The mechanism of biosynthesis of ephedrine coupling with the C1-fragment incorporation is discussed.
The purple fluorescent substance (V-compound) obtained by the authors from the mycelium of Er. ashbyii occurs as colorless needles, m. p. 263°(decomp.), [α]20D : +4.5°(in H2O), +11.45°(in 0.1N NaOH). The molecular weight of this substance was found to be about 300 by Barger method, titration (as monobasic acid), and from the wave height in polarography. A molecular formula of C12H16O7N4 was assigned to the substance from its analytical value. From its ultraviolet and infrared spectra the presence of a pteridine ring, COOH, and OH was presumed. Since the substance gave urea by treatment with alkali solution, it was assumed to be a pteridine compound having a carbonyl group at 2-position, substituted by a group at one of the nitrogens in the pyrazine ring. From the fact that the acetylation product of the substance was in accord with its tetraacetate, and that it gave formaldehyde by oxidation with lead tetraacetate, the group was presumed to be ribityl. Photodecomposition of this substance furnished more important data. Although exposure of an aqueous solution of the substance to direct sunlight destroyed even the pteridine ring, irradiation of its alkaline solution with light from an electric lamp in the presence of hydrogen peroxide yielded crystals of m. p. >360°. The product exhibited the ultraviolet spectrum characteristic to pteridine compounds. Comparison of the product with lumazine-6-carboxylic acid by ionophoresis indicated that the former has lower negative charge than the latter. Therefore, the molecular formula, C7H6O4N4, calculated from the analytical value was concluded to be C7H4O3N4·H2O. This may be due to the dehydrogenation of the parent ring during cleavage of the group at the nitrogen of the pyrazine ring by photodecomposition of the V-compound. From these results, the authors gave the following structure to the V-compound.
Durch katalytische Reduktion von 1-Aminoisochinolin mit PtO2 in Eisessig-Losung wurde 1-Amino-5, 6, 7, 8-tetrahydroisochinolin in 70%iger Ausbeute erhalten. Das letztere wurde nach Grewe in 1-Brom-5, 6, 7, 8-tetrahydroisochinolin mit einer Ausbeute von 71% ubergefuhrt. 1-Amino-5, 6, 7, 8-tetrahydroisochinolin gab beim Diazotieren 5, 6, 7, 8-Tetrahydroisocarbostyril in einer Ausbeute von 90%, welches auch durch direkte Reduktion von Isocarbostyril in einer Ausbeute von 40% erhalten wurde. 5, 6, 7, 8-Tetrahydroisocarbostyril gab beim Erhitzen mit Phosphoroxychlorid 1-Chlor-5, 6, 7, 8-tetrahydroisochinolin mit einer Ausbeute von 80%.
Amongst numerous color tests for essential oil components present, 10% chloroform or ethylene dichloride with 0.01% iodine solution of antimony pentachloride was regarded to be most excellent so far as the instantaneous spot test was concerned. The majority of compounds belonging to the category of essential oil constituents produced characteristic colors by merely touching the reagent to the sample on filter paper, without any additional treatment.
4'-Hydroxy-4-formyl-, 4'-Carboxy-4-formyl- und 4, 4'-Diformyldiphenylather wurden aus den entsprechenden Methyldiphenylathern uber Bromverbindungen synthetisiert und deren Thiosemicarbazone dargestellt.