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Michiya Kimura
1955 Volume 3 Issue 2 Pages
75-80
Published: April 20, 1955
Released on J-STAGE: February 19, 2008
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1)The absorption spectra were measured of the color reaction between each of the fourteen 1-substituted 2, 4, 6-trinitrobenzene compounds and acetone in the presence of alkali. The typical absorption curves are shown in Fig. 1. 2) Phenyl picrate and picryl chloride were selected from among these nitro compounds as examples. When the colored substances, formed by the reaction between each of these two compounds and acetone in alkaline medium, were acidified in the presence of hydrogen peroxide, the trinitrobenzene compounds (III) and (VI) were respectively formed. From this result, the structures (II and V) of these colored substances were determined. 3) The colored substances derived from 1-substituted 2, 4, 6-trinitrobenzene compounds of type A were assumed to form principally the structure of (XVI), while the compounds of type B give both structures of (XVI) (mainly) and (XVII).
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Michiya Kimura
1955 Volume 3 Issue 2 Pages
81-83
Published: April 20, 1955
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The absorption spectra of the colored substances derived from the reaction between picric acid and active methylene compounds (acetone, creatinine, and digitoxin) in the presence of alkali were measured (cf. Fig. 1-1 and Fig. 3) and the chemical structures of these colored complex anions were proposed as shown by formulae (III), (IV), and (V).
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Saburo Hara, Jun Sato
1955 Volume 3 Issue 2 Pages
84-87
Published: April 20, 1955
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The nature of the inhibition of blood coagulation by rare earth metals in vitro is their action on prothrombin in the blood and to inhibit its activation to thrombin. Such action in vivo includes, besides the same direct action on blood, their action on the liver cells to inhibit the formation of prothrombin.
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Michimasa Izumi
1955 Volume 3 Issue 2 Pages
88-91
Published: April 20, 1955
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A cyclization of β-chloroethyl group of N-bis(β-chloroethyl) amino acids and their N-oxides in a dilute aqueous solution was discussed in this paper. The intermediates formed in the solution, viz., ethyleneimonium ions from the tertiary amines or 1, 2-dimethyleneoxaimonium ions (oximonium ions) from the N-oxides, were found to be less stable and more readily subjected to hydrolysis than that of methyl-bis (β-chloroethyl)amine and its N-oxide.
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Torizo Takahashi, Yoshifumi Maki
1955 Volume 3 Issue 2 Pages
92-96
Published: April 20, 1955
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1) Synthesis of derivatives of 6-chloropyrido[2, 3 : 2', 3']-p-thiazine, 5'-oxo-5', 6'-dihydropyrido[2, 3 : 2', 3']-p-thiazine, pyrido[3, 4 : 3', 2']-p-thiazine, and 2-azaphenothiazine was described. 2) Some of their chemical properties, especially their behavior to acids and alkalis, were investigated. 3) The reaction using 2-mercapto-3-amino-6-chloropyridine as one of the starting materials often afforded the by-product of orange rhombics, m.p.210°, which was proved to be 3, 3'-diamino-6, 6'-dichlorodipyridyl 2, 2'-disulfide.
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Masao Tomita, Yasuo Inubushi, Eiichi Fujita
1955 Volume 3 Issue 2 Pages
97-99
Published: April 20, 1955
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The purity and homogeneity of the sample of oxyacanthine showing m.p.210∼213° or 214∼216°(in vacuum), [α]
24D : +276.1°(CHCl
3), employed in our previous work was examined by paper chromatography, etc. These techniques afforded no evidence that it was accompanied with its optical isomer, repandine. The conditions under which repandine may form from oxyacanthine by treatment with hydrogen chloride was also investigated using the same sample of oxyacanthine but furnished no evidence for tis contamination with repandine. As a result, it was established that the action of 1.12 moles of hydrogen chloride upon 1 mole of oxyacanthine invariably gave repandine.
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Masao Tomita, Tohru Kikuchi
1955 Volume 3 Issue 2 Pages
100-104
Published: April 20, 1955
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The tertiary base, dauricine, of Menispermum dauricum DC. had already been studied in detail and its chemical structure established, but the investigation of the quaternary bases present had been left undone. In this paper, the isolation of two quaternary bases from the same plant is presented. One of these bases, which occurs in comparatively larger amounts, was named menisperine. It was found that menisperine iodide is identical with d-isocorydine methiodide. For the representation of menisperine formula (V) of the aporphine type may be considered as appropriate.
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Teiji Ukai, Yuzuru Yamamoto, Shozo Hirano, Masaru Yotsuzuka
1955 Volume 3 Issue 2 Pages
105-108
Published: April 20, 1955
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1) The mercuration of diphenylsulfone with mercuric acetate was found to occur in the 2-position. 2) Following reaction mechanism was proposed for aromatic mercuration. i) Aromatic mercuration, as a rule, is an electrophilic reaction. ii) When mercurating the compound possessing a substituent which has lone-pair electrons, the initial coordination of the mercury atom with the substituent, and the transient ring complex formation by the approach of the mercury atom to an appropriate carbon atom, if any, in the nucleus might take place. It is then that the substitution occurs. It is therefore clear that spatial condition is the determining factor as to where it is mercurated. When the coordination is impossible or has no effect, the reaction proceeds just as in other electrophilic substitution reaction.
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Genshun Sunagawa, Takeshi Ichii, Norio Yoshida
1955 Volume 3 Issue 2 Pages
109-115
Published: April 20, 1955
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Benzylamine derivatives possessing a substituent of marked +M effect (e.g. methoxyl, hydroxyl, dimethylamino, methylenedioxy) in the para- or ortho-position of the benzyl group and an aromatic residue (e.g. phenyl, pyridyl, pyrimidyl) attached to the amino nitrogen were shown to undergo facile decomposition by mineral acids to form benzyl alcohol, diphenylmethane, or dihydroanthracene derivatives and aromatic amines.
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Genshun Sunagawa
1955 Volume 3 Issue 2 Pages
116-124
Published: April 20, 1955
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The compounds of the general formula [chemical formula], where R is a substituent with +M effect in the ortho- or para-position of -CH
2-, R' is H or alky l (or aminoalkyl) group, and R" is an aromatic residue, when heated with dilute hydrochloric acid, are cleaved first into benzyl alcohol and an aromatic amine. When the reaction proceeds further, a diphenylmethane compounds are formed by the aromatic electrophilic substitution of the following order : [chemical formula] In some cases, the aromatic amine liberated in the first stage of the reaction takes part in the second stage of the reaction which proceeds in the following order, as had earlier been recognized.
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Genshun Sunagawa
1955 Volume 3 Issue 2 Pages
124-131
Published: April 20, 1955
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1) The reaction between p-X-C
6H
4-CH
2OH (X=substituent with +M effect) and p-Y-C
6H
5 (Y=substituent with +M effect) in acid was examined and it was found that products formed in the case of X=CH
3O were mainly [chemical formula] and [chemical formula], while in the case of X=(CH
3)
2N and H
2N, [chemical formula] is chiefly formed. 2) p-Methoxybenzyl alcohol undergoes aromatic electrophilic substitution with [chemical formula] and hydrochloric acid. 3) The reaction mechanism whereby diphenylmethane is formed by the aromatic electrophilic substitution of [chemical formula] has been clarified.
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Hisakichi Matsumura, Sadao Iguchi, Shigeru Miyamoto, Magobei Yamamoto
1955 Volume 3 Issue 2 Pages
131-137
Published: April 20, 1955
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1. By employing the concentric cylinder method, rheological studies were made both on the thixotropy of the peanut oil-aluminum stearate system, the most commonly used base for penicillin injection, and also on the castor oil-aluminum stearate system for the sake of comparison. 2. Peanut oil and castor oil containing no aluminum stearate showed the Newtonian flow. The mechanical behaviours of the oil-aluminum stearate system were expressed by mechanical models. 3. The mechanical models of the system containing aluminum stearate (up to 2%) in peanut oil were as follows. Immediately after stirring, the sample behaves as a pure viscous flow (Newtonian flow), whose viscosity coefficient was very high compared to the oil containing no aluminum stearate. This model became the Maxwell model with Newtonian flow and then it turned into the Maxwell model with non-Newtonian flow in the course of time. On the other hand, the model for the castor oil system containing aluminum stearate (up to 2%) was always Newtonian flow, and neither elasticity nor non-Newtonian flow was observed in the course of time after-standing of the sample.
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Yuichi Kamura
1955 Volume 3 Issue 2 Pages
138-143
Published: April 20, 1955
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Studies on the theory of high-frequency analysis are becoming numerous but some of their reports contain doubtful points as to the formulation of such theories. The present studies were made in order to examine the method of theoretical formulation and it has become clear that different experimental results are obtained from identical phenomena according to the method of measurements employed. In formulating a theory in high-frequency analysis, the point to note is the actual method of measurements. In other words, a theoretical formulae which agree with the method of measurements must be obtained. The variations of electric current, electric voltage, and cycles measured by oscillating or receiver type cannot be directly explained by the results obtained through measurement by the bridge. In order to explain theoretically the experimental results obtained by the analytical apparatus currently used, high frequency wave was directly applied to solutions and the nature of the changes were examined by the bridge. Correlation of such a change and indirect measurement through the wall of the beaker was sought. Based on there results, a theoretical formula which would support the method of measurements by the currently used analytical apparatus was obtained. By making concrete calculations, uniform explanations for concentration curves in general were made. Some improvements were also made for drawing up theoretical curves for the existing indirect measurement.
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Kakuma Nagazawa, Einosuke Koshimura, Seiichi Okazaki
1955 Volume 3 Issue 2 Pages
144-147
Published: April 20, 1955
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Two-and-two dose assay method was applied for the quantitative analysis of estrone and estradiol by paper chromatographic analysis, measuring the area of spots, and fairly satisfactory results were obtained. In a fresh urine of a pregnant mare, an average 2% of free estrone and 6% of free estradiol, 98% of conjugate estrone, and 94% of conjugate estradiol were found by this method. About equal amounts of estrone (39 γ/cc.) and estradiol (40 γ/cc.) were determined in the stored stallion urine.
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Morizo Ishidate, Takeichi Sakaguchi
1955 Volume 3 Issue 2 Pages
147-155
Published: April 20, 1955
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Aureomycin forms chelate compounds with various metals, especially stable compounds with zirconium (IV), thorium (V), uranium (VI), aluminum, and magnesium. Cobalt and copper are also capable of forming the chelate compound with the antibiotic. A comparison of Aureomycin-metal chelates with 1-hydroxyanthraquinone chelates was made spectrophotometrically. The results of this experiment proved that the presence of the constituent functional groups, a peri-standing phenolic hydroxyl and carbonyl, in Aureomycin was important. The molar ratio of these complexes containing Zr, Th, or UO
2 was determined by the continuous variation method of Job, and structural formulae of these complexes are suggested. It is believed that some of these chelates may offer a sensitive method for the chemical determination of Aureomycin and the allied compounds.
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Shoji Shibata, Michio Takido
1955 Volume 3 Issue 2 Pages
156-158
Published: April 20, 1955
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Zen-ichi Horii, Tatsuo Sakai, Takeshi Inoi
1955 Volume 3 Issue 2 Pages
159
Published: April 20, 1955
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Shoji Shibata, Takao Murakami, Osamu Tanaka, Goro Chihara, Isao Kitaga ...
1955 Volume 3 Issue 2 Pages
160-161
Published: April 20, 1955
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