YAKUGAKU ZASSHI
Online ISSN : 1347-5231
Print ISSN : 0031-6903
ISSN-L : 0031-6903
79 巻, 8 号
選択された号の論文の30件中1~30を表示しています
  • β-(2, 5-Dimethoxyphenyl)-β-hydroxyisopropylamineの合成
    里田 勲, 楠田 冬樹, 尾本 敏寿, 川真田 正信, 山本 泰男
    1959 年 79 巻 8 号 p. 989-992
    発行日: 1959/08/25
    公開日: 2010/02/19
    ジャーナル フリー
    β-(2, 5-Dimethoxyphenyl)-β-hydroxyisopropylamine hydrochloride (VII), the sympathetic nerve stimulant, is adopted in the U. S. Pharmacopea as methoxamine hydrochloride and is used as vascular contraction and hypertensive agent. Its synthesis was limited to the route shown in Chart 1 but in order to find industrial process other method of synthesis was examined and a new process, shown in Chart 2, was devised. This process utilizes Gabriel condensation and Meerwein-Ponndorf reduction, the procedure is simple, and the yield is good that it seems to be a very advantageous industrial process. It was also found during the course of this synthesis that by exchanging the order of reduction and cleavage of the condensate, either of the threo or erythro diastereomers is formed. The conformation of these products will be discussed in detail in the forthcoming report but N→O acetyl migration was showed the same result as that seen in ephedrine chemistry.
  • えぞばいけい草からZygadenilic Acid δ-Lactoneの分離
    清水 文治
    1959 年 79 巻 8 号 p. 993-997
    発行日: 1959/08/25
    公開日: 2010/02/19
    ジャーナル フリー
    The minor alkaloid contained in Veratrum oxysepalum growing in the Hokkaido, the so-called C-base, was proved to be a δ-Lactone of zygadenilic acid. In other words, this base agrees with the product formed by oxidation of ψ-zygadenine with bismuth oxide. The acetonide of this base on the other hand agrees with the product obtained by similar oxidation of isozygadenine 14, 15-acetonide.
  • 富田 真雄, 北村 為男
    1959 年 79 巻 8 号 p. 997-1003
    発行日: 1959/08/25
    公開日: 2010/02/19
    ジャーナル フリー
    Trimethoxyaporphines (I) with methoxyls each in 1- and 2-positions and another methoxyl in 8-, 10-, or 11-position have already been synthesized, but not the one with the third methoxyl in 9-position. In the present series of work, 1, 2, 9-trimethoxyaporphine (II) was synthesized by the route shown in Chart 1. During the course of this synthesis, Pschorr's phenanthrene cyclization of the amine (IX) was found to produce the cleaved fragments, 2-methyl-6, 7-dimethoxy-1, 2, 3, 4-tetrahydroisoquinoline (X) and 5-methoxyindiazole (XI), besides the objective aporphine-type base (II), as well as trace amounts of a few other substances. There is a report that a diazo compound (XVI) is formed by diazotization of aminopapaverine (XV). In the present work, this reaction was followed by the formation of an intermediate (XVII) was assumed as a result of side reaction but the compound was not actually isolated. However, this intermediate may be assumed to undergo cleavage reaction, producting the two decomposition products, (X) and (XI). Example of such reaction is not found in any of the past literature.
    Further, one-dimensional paper chromatography of dl-1, 2, 9-trimethoxyaporphine (II) was carried out and two spots of approximately the same size and intensity were produced (Fig. 2). This is thought to be due to dissolution of racemate by paper chromatography, as has deen reported in the literature. 5-Methoxyindiazole (XI) obtained as a by-product in the present reaction is a new substance not yet reported in any literature and the compound was synthesized by the route shown in Chart 2.
  • 9,10-Dimethoxy-1,2,3,4,6,7-hexahydro-11bH-pyrazo[2,1-a] isoquinoline類の合成
    山崎 高応
    1959 年 79 巻 8 号 p. 1003-1008
    発行日: 1959/08/25
    公開日: 2010/02/19
    ジャーナル フリー
    1-Aminomethyl-6, 7-dimethoxy-1, 2, 3, 4-tetrahydroisoquinoline, obtained by the author's improved method, was reacted with ethylene bromide and gave 9, 10-dimethoxy-1, 2, 3, 4, 6, 7-hexahydro-11bH-pyrazo[2, 1-a] isoquinoline (VI). Reductive methylation of (VI) with formaldehyde and formic acid afforded 2-methyl-9, 10-dimethoxy-1, 2, 3, 4, 6, 7-hexahydro-11bH-pyrazo[2, 1-a] isoquinoline (VII), which was also obtained by the Bischler-Napieralski reaction of 1-homoveratryl-4-methyl-2-oxopiperazine, formed by the Tafel electrolytic reduction of the corresponding 2, 6-dioxopiperazine, followed by catalytic reduction over platinum oxide catalyst. Physiological actions of the hydrochlorides of (VI) and (VII) are now being examined.
  • 9,10-Dimethoxy-1,2,3,4,6,7-hexahydro-11bH-pyrimido [4,3-a] isoquinoline類の合成
    山崎 高応
    1959 年 79 巻 8 号 p. 1008-1013
    発行日: 1959/08/25
    公開日: 2010/02/19
    ジャーナル フリー
    Reaction of 1-ethoxycarbonylmethyl-6, 7-dimethoxy-1, 2, 3, 4-tetrahydroisoquinoline with urea gave 2, 4-dioxo-9, 10-dimethoxy-1, 2, 3, 4, 6, 7-hexahydro-11bH-pyrimido [4, 3-a]-isoquinoline (II), which was reduced to 9, 10-dimethoxy-1, 2, 3, 4, 6, 7-hexahydro-11bH-pyrimido [4, 3-a] isoquinoline (III) with lithium aluminum hydride at 60°, but to 1-methyhlaminoethyl-6, 7-dimethoxy-1, 2, 3, 4-tetrahydroisoquinoline (IV) at 80°. Reductive methylation of (III), suffering fission of the hydropyrimidine ring, with formaldehyde and formic acid, or by formaldehyde and hydrogenation over Raney nickel under high pressure, gave 1-(2-dimethylaminoethyl)-2-methyl-6, 7-dimethoxy-1, 2, 3, 4-tetrahydroisoquinoline (V), identical with the compound obtained by the reaction of (IV) with formaldehyde and formic acid. Hydrolysis of (III), with mineral acid gave 1-(2-aminoethyl)-6, 7-dimethoxy-1, 2, 3, 4-tetrahydroisoquinoline (VIII), which was reversibly converted into (III) on treatment with formaldehyde. Reaction of (IV) with formaldehyde or vanillin gave 3-methyl-9, 10-dimethoxy-1, 2, 3, 4, 6, 7-hexahydro-11bH-pyrimido [4, 3-a] isoquinoline (VI), the N-methyl compound of (III), or 3-methyl-4-(3′-methoxy-4′-hydroxyphenyl)-9, 10-dimethoxy-1, 2, 3, 4, 6, 7-hexahydro-11bH-pyrimido [4, 3-a] isoquinoline (VII). The products, (VI) and (VII), were also hydrolysed into the starting material (IV), respectively liberating formaldehyde and vanillin. The compound (III), a hydropyrimidine derivative, was readily acylated or tosylated without suffering fission of the ring, which differs from an imidazolidine derivative. Physiological actions of (II), (III), (IV), (V), (VI), and (VII) are to be examined.
  • 9,10-Dimethoxy-1,2,3,4,6,7-hexahydro-11bH-pyrimido [2,1-a] isoquinoline類の合成
    山崎 高応
    1959 年 79 巻 8 号 p. 1014-1018
    発行日: 1959/08/25
    公開日: 2010/02/19
    ジャーナル フリー
    N-(2-Cyanoethyl)-3, 4-dimethoxyphenethylamine, obtained by cyanoethylation of 3, 4-dimethoxyphenethylamine with acrylonitrile, was derived to a urethan by ethyl chlo-rocarbonate. The urethan was hydrogenated over Raney nickel catalyst under high pressure, followed by ring closure, to 1-(3, 4-dimethoxyphenethyl) hexahydropyrimid-2-one (IV), which was cyclized to 9, 10-dimethoxy-1, 2, 3, 4, 6, 7-hexahydropyrimido [2, 1-a] isoquinolinium chloride (V) with phosphorous pentoxide and phosphoryl chloride and phosphoryl chloride. (V) was reduced to the corresponding pyrimido [2, 1-a] isoquinoline derivative (VI) with lithium aluminum hydride but was reduced to 10, 11-dimethoxy-1, 2, 3, 4, 5, 6, 7, 8-octahydro-2, 6-benzodiazocine (VI′) with sodium borohydride. Treatment of (VI) with hydrochloric acid gave 2-(3-aminopropyl)-6, 7-dimethoxy-3, 4-dihydroisoquinolinium chloride (VIII) which was hydrogenated to 2-(3-aminopropyl)-6, 7-dimethoxy-1, 2, 3, 4-tetrahydro-isoquinoline (IX). Physiological actions of (V), (VI), (VI′), (VIII), and (IX) are to be examined.
  • dl-3,4´-Bis (2-methyl-6,7-dimethoxy-1,2,3,4-tetrahydro-1-isoquinolylmethyl) diphenyl Etherの合成
    富田 真雄, 新美 仁作
    1959 年 79 巻 8 号 p. 1019-1022
    発行日: 1959/08/25
    公開日: 2010/02/19
    ジャーナル フリー
    Biscoclaurine-type bases were prepared by the Ullmann reaction of two kinds of benzyl-tetrahydroisoquinoline-type bases. One of the starting materials, 1-(3-hydroxybenzyl)-2-methyl-6, 7-dimethoxy-1, 2, 3, 4-tetrahydroisoquinoline (VI) was prepared and it was submitted to the Ullmann condensation with 1-(4-bromobenzyl)-2-methyl-6, 7-dimethoxy-1, 2, 3, 4-tetrahydroisoquinoline (VIII) to form the fundamental skeleton of the dauricine-type bases, i.e. dl-3, 4′-bis (2-methyl-6, 7-dimethoxy-1, 2, 3, 4-tetrahydro-1-isoquinolylmethyl) diphenyl ether (IX).
  • 富田 真雄, 新美 仁作
    1959 年 79 巻 8 号 p. 1023-1027
    発行日: 1959/08/25
    公開日: 2010/02/19
    ジャーナル フリー
    Heating of 1-(3, 4-methylenedioxybenzyl)-6, 7-dimethoxy-1, 2, 3, 4-tetrahydroisoquinoline (IV) with a mixture of formic acid and formaldehyde affords 2, 3-dimethoxy-10, 11-methylenedioxy-5, 6, 13, 13a-tetrahydro-8H-dibenzo [a, g] quinolizine (V) (tetrahydro-ψ-epiberberine). Cleavage of its methylenedioxy group by application of metallic sodium to (V) in liquid ammonia afforded a phenolic base. A protoberberine-type base was prepared from 1-(3-hydroxybenzyl)-6, 7-dimethoxy-1, 2, 3, 4-tetrahydroisoquinoline (X) and the two bases here obtained were found to be identical. Consequently, the phenolic base obtained by cleavage of tetrahydro-ψ-epiberberine (V) with sodium in liquid ammonia was proved to be 2, 3-dimethoxy-11-hydroxy-5, 6, 13, 13a-tetrahydro-8H-dibenzo [a, g] quinolizine (VI).
  • 小型偏光顕微鏡を装着した新微量融点測定装置について
    穂積 啓一郎, 森田 舒子
    1959 年 79 巻 8 号 p. 1028-1034
    発行日: 1959/08/25
    公開日: 2010/02/19
    ジャーナル フリー
    Detailed description is given for micro-apparatus for melting point determination in which ×10 magnifying glass and ×60 polaroid microscope can be used alternately. This apparatus, as illustrated in Figs. 1 and 2, is provided with a hot stage, voltage adjuster, and an optical mechanism for reading the temperature, assemblied on a metal body. The hot stage is comparatively small and the temperature response to voltage variation is rapid. It is also convenient to be able to observe the sample with the right eye and read the temperature graduation inside the finder with the left eye. The sample scattered on the hot stage can be observed through the magnifying glass and a microscopic observation can be made on the light well in the center. The hot stage is also provided with a long groove to admit a capillary tube and a round hole for microsublimation. The observed value is corrected as follows: When the rate of heating is controlled at 2°/min., (1) the error of a thermometer is subtracted from the temperature indicated by the thermometer, with the sample on the flat surface of the hot stage or in a capillary; and (2) when the sample is on the light well, the thermometer error is subtracted from the thermometer reading, and the value of 0.5° for melting point up to 100°, 10° for that in the range of 100-200°, and 1.5°, for that above 200°, is subtracted from the foregoing value.
  • テトラロン誘導体の酸化によるナフトキノン誘導体の合成 その1
    庄司 達雄
    1959 年 79 巻 8 号 p. 1034-1038
    発行日: 1959/08/25
    公開日: 2010/02/19
    ジャーナル フリー
    Oxidation of α-tetralone in glacial acetic acid with chromium trioxide affords 1, 2-naphthoquinone while the same oxidation of 2-methyl-α-tetralone gives 2-methyl-1, 4-naphthoquinone. These reactions show that a quinone was produced from an alicyclic compound. On the other hand, oxidation of 5, 8-dihydroxy-α-tetralone derivative with ferric chloride in dilute acetic acid affords 8-hydroxy-1, 4-naphthoquinone derivative. In this case, aromatic ring changes into a quinone while the alicyclic ring is aromatized and the carbonyl changes into a hydroxyl. By the same oxidation, 5, 8-dihydroxytetralone produced juglone, 7-methyl-5, 8-dihydroxytetralone gave 2-methyl-8-hydroxy-1, 4-naphthoquinone, 5, 8-dihydroxytetralone-2-acetic acid gave 8-hydroxy-1, 4-naphthoquinone-7-acetic acid, 2, 7- and 3, 7-dimethyl-5, 8-dihydroxytetralone gave 2, 7- and 2, 6-dimethyl-8-hydroxy-1, 4-naphthoquinone, and 2, 2, 7-trimethyl-5, 8-dihydroxytetralone did not submit to this oxidation. The interesting fact is that the oxidation of 2, 7-dimethyl-5, 8-dihydroxytetralone with silver oxide afforded 2, 7-dimethyl-8-oxo-5, 6, 7, 8-tetrahydro-1, 4-naphthoquinone, and 2, 2, 7-trimethyl-5, 8-dihydroxytetralone afforded 2, 7, 7-trimethyl-8-oxo-5, 6, 7, 8-tetrahydro-1, 4-naphthoquinone. This process of oxidation with ferric chloride will enable shortening of the past method for synthesis of 8-hydroxy-1, 4-naphthoquinone derivatives by several steps.
  • テトラロン誘導体の酸化によるナフトキノン誘導体の合成 その2
    庄司 達雄
    1959 年 79 巻 8 号 p. 1038-1041
    発行日: 1959/08/25
    公開日: 2010/02/19
    ジャーナル フリー
    The alkyl group in 7-alkyl-5, 8-dihydroxy-α-tetralone was extended from C2 to C10 and their oxidation with ferric chloride was examined. It was found that oxidation is effected irrespective of the length of alkyl group and 2-alkyl-8-hydroxy-1, 4-naphthoquinone derivatives are obtained in good yield. The melting point of these quinone derivatives increase with increasing molecular weight, the melting points rising or falling alternately with even and odd number of carbon atoms, and compounds with even number of carbon atoms showed higher melting point than those with odd numbers. Such tendency was not observed with intermediates other than quinone derivatives.
  • 8-オキシナフトキノン誘導体の抗菌性
    庄司 達雄
    1959 年 79 巻 8 号 p. 1041-1044
    発行日: 1959/08/25
    公開日: 2010/02/19
    ジャーナル フリー
    Growth inhibition of 8-hydroxy-1, 4-naphthoquinone derivatives was examined with bacteria and fungi. These derivatives generally showed a wide antibacterial spectrum and 2, 7-dimethyl-8-hydroxy-1, 4-naphthoquinone showed inhibition against growth of staphylococci and coli bacilli in 1, 024, 000 dilution. This was followed by the activity of 2-methyl-8-hydroxy-1, 4-naphthoquinone and juglone. For comparison of growth inhibitory action, 2-methyl-3, 8-dihydroxy-1, 4-naphthoquinone was obtained by oxidation of 2-methyl-8-hydroxy-1, 4-naphthoquinone with hydrogen peroxide in sodium carbonate solution to form an oxide and its treatment with dilute sulfuric acid.
  • 8-オキシ-1,4-ナフトキノン誘導体の金属キレート化合物
    庄司 達雄
    1959 年 79 巻 8 号 p. 1044-1047
    発行日: 1959/08/25
    公開日: 2010/02/19
    ジャーナル フリー
    Reaction of 8-hydroxy-1, 4-naphthoquinone derivatives and metal ion was carried out and formation of chelate compounds was detected by photochemical method. Copper chelates of a few compounds were isolated and their structure was examined. The copper chelates of 2-alkyl-, and 2, 7- and 2, 6-dimethyl-8-hydroxy-1, 4-naphthoquinones were determined to have quinone to copper ratio of 2:1 by gravimetric method. These chelates were also found to be in 2:1 ratio in solution as determined by the Job method. These chelate compounds dissolve in pyridine, chloroform, and carbon tetrachloride to form a red solution but their solubility in the solvent depends on length of the alkyl chain. The chelates regenerate the quinone by acid and they are labile in solution state. Ultraviolet spectra of quinone derivatives show absorption maxima at 419-423 and 266-270mμ in 2-alkyl compounds, at 422 and 261mμ in 2, 6-dimethyl compound, and at 432 and 261mμ in 2, 7-dimethyl compound. The copper chelates of these compounds show absorption maximum at 502-515mμ, indicating shift to a longer wave-length region, but there was no special regularity of the shift with the length of alkyl chain.
  • 4-Alkyl-2-pyrrolecarboxylic Acid誘導体の合成研究
    海尾 澄則
    1959 年 79 巻 8 号 p. 1048-1052
    発行日: 1959/08/25
    公開日: 2010/02/19
    ジャーナル フリー
    Syntheses of 2-pyrrolecarboxylic acids possessing a substituent that can be derived to carboxymethyl group in 3-position were undertaken. Condensation of ethyl 2-amino-2-isobutyrylacetate and ethyl acetopyruvate resulted in the liberation of isobutyryl group, irrespective of acid or alkaline medium, and 2, 3-diethoxycarbonyl-5-methylpyrrole was produced. This reaction has indicated that in this kind of condensation reaction, liberation of acetyl group from ethyl acetopyruvate as reported to date is not correct and that the liberation of the acetyl group is from the corresponding ethyl 2-amino-acetoacetate. A process for preparation of a new type 2-pyrrolecarboxylic acids possessing α-ketoacetal group in 3-position was found by the condensation of α-aminoketones with ethyl 2, 4-dioxo-5-dimethoxyvalerate. The reduction of the ketone group in the α-ketoacetal group to methylene was examined and the objective methyl 3-(2-dimethoxyethyl)-4-isopropyl-2-pyrrolecarboxylate was obtained.
  • 廻 治雄
    1959 年 79 巻 8 号 p. 1052-1056
    発行日: 1959/08/25
    公開日: 2010/02/19
    ジャーナル フリー
    Toxic components were extracted from the flowers of Pieris japonica D. DON., forming colorless silky crystals of m.p. 217-218°, C20H32O7, colorless needles of m.p. 257°, C22H32O8, and colorless rhomboprismatic crystals of m.p. 262°, C24H38O9. These were considered to be new components and were termed pieristoxin-A, -B, and -C. These three components undergo reactions as indicated in Chart 1 but pieristoxin-A does not contain an acetyl group, while pieristoxin-B contains one acetyl and pieristoxin-C, two acetyl groups.
  • 廻 治雄
    1959 年 79 巻 8 号 p. 1057-1059
    発行日: 1959/08/25
    公開日: 2010/02/19
    ジャーナル フリー
    Toxic desacetylandromedotoxin (grayanotoxin III) and pieristoxin C were isolated from the leaves of Pieris japonica D. DON.. Extraction and isolation of grayanotoxin III from a plant is the first example.
  • 廻 治雄
    1959 年 79 巻 8 号 p. 1060-1062
    発行日: 1959/08/25
    公開日: 2010/02/19
    ジャーナル フリー
    Desacetylation of andromedotoxin (grayanotoxin I) to desacetylandromedotoxin (grayanotoxin III) and its treatment with anhydrous copper sulfate in acetone, as shown in Chart 1, showed that the monoanhydro compound is identical with grayanotoxin II. Interrelationship between andromedotoxin (grayanotoxin I) and grayanotoxin II was clarified.
  • 2-Aminochinolin-N-oxyd, 1-Aminoisochinolin-N-oxydの合成およびその性質
    谷田 博
    1959 年 79 巻 8 号 p. 1063-1068
    発行日: 1959/08/25
    公開日: 2010/02/19
    ジャーナル フリー
    2-Aminoquinoline 1-oxide and 1-aminoisoquinoline 2-oxide were prepared and the nature of their respective amino group was examined. Conversion of these compounds to N-oxide compounds with nitro and other negative groups was attempted but did not materialize.
  • Dimethylagrimononeの合成
    大和 正利
    1959 年 79 巻 8 号 p. 1069-1073
    発行日: 1959/08/25
    公開日: 2010/02/19
    ジャーナル フリー
    It was concluded that the structure of agrimonolide (I), [α]D5 +8.1°, would be formulated as (II), (III), or (IV), but (II) is a phthalide and its C=O vibration should be around 5.7μ, that of 6.05μ in (I) being too much to the longer wave-length region even with consideration of hydroxyl at 7-position. Infrared spectra (in Nujol) of natural dihydroisocoumarins showed this absorption at 6.04μ in hydrangenol (XIII) and 6.04μ in phyllodulcin (XIV), which are in good agreement with that of (I) and of monomethylagrimonolide (V) at 6.04μ (in Nujol), while that of bergenin (XII) at 5.88μ (Nujol) agrees with that of dimethylagrimonolide. This suggests that (I) is either (III) or (IV).
    The two phenolic hydroxyls in agrimonol (XV), obtained by saponification of (I) followed by decarboxylation, were methylated with diazomethane and cautious oxidation of the methylated product afforded dimethylagrimonone and cautious oxidation of the methylated product afforded dimethylagrimonone (XVII) which was found to agree with 3, 5-dimethoxybenzyl p-methoxyphenethyl ketone (XIX), prepared by the route shown in Chart 2, by comparison of their 2, 4-dinitrophenylhydrazone, m.p. 104°. Consequently, (I) was proved to be d-3-(p-methoxyphenethyl)-6, 8-dihydroxy-3, 4-dihydroisocoumarin (III).
  • 6-,7-および8-Methyl-5,6,7,8-tetrahydroquinolineならびに6-,7-および8-Methylquinolineの合成
    石黒 武雄, 森田 善夫, 生嶋 和雄
    1959 年 79 巻 8 号 p. 1073-1079
    発行日: 1959/08/25
    公開日: 2010/02/19
    ジャーナル フリー
    A process was found whereby methyl-5, 6, 7, 8-tetrahydroquinoline and methylquinoline are synthesized at the same time by catalytic vapor-phase reaction of methyl-cyclohexanone, allyl alcohol, and ammonia with cadmium phosphate as the catalyst. 4-Methylcyclohexanone (I) afforded 6-methyl-5, 6, 7, 8-tetrahydroquinoline (II) and 6-methylquinoline (III), while 3-methylcyclohexanone (IV) afforded 7-methyl-5, 6, 7, 8-tetra-hydroquinoline (V) and 7-methylquinoline (VI). However, 3-methylcyclohexanone (IV) did not afford the expected 5-methyl derivatives (VII and VIII). In the same manner, 2-methylcyclohexanone (IX) produced 8-methyl-5, 6, 7, 8-tetrahydroquinoline (X) and 8-methylquinoline (XI). In all these reactions, a small amount of 3-picoline and a trace of 3, 5-lutidine were detected as the by-product. The good yield of (II) as compared to that of (V) and (X) was discussed in comparison with numerous examples of the preparation of 2, 3-alkylated derivatives of pyridine described in the preceding paper.
  • ワルファリンの螢光分析
    市村 陽二
    1959 年 79 巻 8 号 p. 1079-1082
    発行日: 1959/08/25
    公開日: 2010/02/19
    ジャーナル フリー
    Based on the fact that coumarin derivatives show fluorescence, fluorometric analysis of these compounds was attempted. As the first step, examination was made with Warfarin, the coumarin rodenticide. Warfarin shows dark blue fluorescence. Energy distribution of this fluorescence was measured and a filter suitable for measurement of this fluorescence intensity was selected from this energy distribution. Examinations were made on the correlation of the solvent used, reaction of the medium, periodical variation, concentration, and fluorescence intensity during measurement with fluorophotometer. It was thereby found that the fluorescence of Warfarin was the strongest and fairly stable in alkaline alcoholic solution and that a linear relationship was found to hold in a certain concentration range.
  • タカトグサ第四級塩基Takatonineの構造
    藤田 栄一, 富松 利明
    1959 年 79 巻 8 号 p. 1082-1086
    発行日: 1959/08/25
    公開日: 2010/02/19
    ジャーナル フリー
    Commercial crude drug, ‘Takato-gusa’, the dried leaves and stems of Thalictrum minus from Nagano Prefecture was examined and a new quaternary base, takatonine, was isolated in a good yield as its iodide (I). Reduction of takatonine iodide with zinc dust and acetic acid afforded 1, 2, 3, 4-tetrahydrotakatonine (II), which was oxidized with potassium permanganate and gave anisic acid (IV). Hofmann degradation of 1, 2, 3, 4-tetrahydrotakatonine methiodide (V) and permanganate oxidation of the resultant methine base afforded anisic acid (IV) and an amino acid (VII). The second Hofmann degradation of this amino acid and subsequent permanganate oxidation of its product afforded 3, 4, 5-trimethoxyphthalic anhydride (X). Comparison of infrared spectra and Rf values in paper chromatography showed tetrahydrotakatonine to be identical with the synthesized dl-O-methylcorpaverine (dl-1-(4-methoxybenzyl)-2-methyl-6, 7, 8-trimethoxy-1, 2, 3, 4-tetrahydroisoquinoline) (II). Ultraviolet spectrum of takatonine iodide was very similar to that of papaverine iodide but entirely different from that of 1, 2-dehydrolaudanosine iodide, from which it was certain that takatonine molecule contained a true isoquinoline ring. Thus, the structure formula (I) was proposed for takatonine iodide.
  • アミノシクロペンタン誘導体について その2
    高橋 酉蔵, 加藤 旭, 松岡 晉
    1959 年 79 巻 8 号 p. 1087-1091
    発行日: 1959/08/25
    公開日: 2010/02/19
    ジャーナル フリー
    In order to examine analgesic activity, 2-diethylaminomethyl-, 2-piperidinomethyl-, and 2-morpholinomethyl-1-alkylcyclopentanols, and their benzoyl and p-nitrobenzoyl esters were synthesized.
  • 南天のアルカロイド その3
    富田 真雄, 北村 為男
    1959 年 79 巻 8 号 p. 1092-1093
    発行日: 1959/08/25
    公開日: 2010/02/19
    ジャーナル フリー
    Examination of Nandina alkaloids has been carried out from olden times and extraction of Nandina has also been reported in numerous examples but there is hardly any distinction between Nandina domestica THUNB. and N. domestica var. leucocarpa MAKINO as the original plant. Extraction was carried out in the present work on the root, stem, and fruit of the two kinds of Nandina separately and comparison was made on the tertiary base extracted. It was thereby learned that both kinds of Nandina contained domesticine and its methyl ether as the main alkaloid, with several of similar bases as minor alkaloids, and that the amount contained in the two plants were approximately the same.
  • 4種のヒヨスチアミン含有植物 (ハシリドコロ, ベラドンナ, ヨウシュチヨウセンアサガオ, ヒヨス) の比較検討
    萩庭 丈寿, 原田 正敏
    1959 年 79 巻 8 号 p. 1094-1096
    発行日: 1959/08/25
    公開日: 2010/02/19
    ジャーナル フリー
    The four kinds of plants containing hyoscyamine (Scopolia japonica MAXIM., Atropa Belladonna L., Datura tatula L., and Hyoscyamus niger L.) are used equally for antispasmodic activity. In order to compare these, methanolic extract of each plant was examined as to alkaloidal content, ratio of the content of scopolamine and hyoscyamine, intra-peritoneal and oral toxicity doses in mice, and antispasmodic action tested by mouse intestine. As a result, it was found that the least toxic was the root of Scopolia japonica and its antispasmodic effect was comparable to hyoscyamine, while the leaves of this plant contained a small amount of the alkaloid and had less antispasmodic effect. Belladonna root and leaves contained a large amount of the alkaloid, had small toxicity, and a strong antispasmodic effect. This plant is considered to be the best among those containing hyoscyamine. Datura leaves also contained a large amount of the alkaloid, although the toxicity was somewhat stronger, and its antispasmodic effect was comparable to belladonna leaves. The leaves of Hyoscyamus niger contained only a very small amount of the alkaloid, had the weakest antispasmodic effect, and a strong toxicity. This plant was therefore the most inferior of these four plants.
  • 富田 真雄, 別所 清
    1959 年 79 巻 8 号 p. 1097-1099
    発行日: 1959/08/25
    公開日: 2010/02/19
    ジャーナル フリー
    Cleavage reaction with metallic sodium in liquid ammonia was carried out with 2, 2′, 3′-trimethoxy-4, 5′-dimethyldiphenyl ether (III), possessing the diaryl ether skeleton similar to those of O-methylpilocereine (Ib) and isotetrandrine (II). As the cleaved product, creosol (V) alone was isolated from the phenolic portion, identified as its 3, 5-dinitrobenzoate, and only veratric acid (VIII) was obtained by permanganate oxidation of the product from the non-phenolic portion. This has revealed that cleavage of (III) by liquid ammonia-sodium specifically attacked the (a) position alone.
  • Dehydroacetic Acidおよび3-Acetyl-4-hydroxycoumarinのアンモニウム塩について
    井口 定男, 後藤 茂, 児玉 康志
    1959 年 79 巻 8 号 p. 1100-1102
    発行日: 1959/08/25
    公開日: 2010/02/19
    ジャーナル フリー
    No reliable report is found on ammonium salts of dehydroacetic acid and 3-acetyl-4-hydroxycoumarin. Therefore, these salts were prepared and their properties were examined. These ammonium salts are comparatively labile and tends to liberate ammonia gradually during storage. The most interesting was their behavior in solution. The solution of the ammonium salt of dehydroacetic acid or 3-acetyl-4-hydroxycoumarin in polar solvent, like water and alcohol, converts into monoimide under a very mild condition.
  • バイケイソウのアルカロイド
    塚本 赳夫, 八木 晟
    1959 年 79 巻 8 号 p. 1102-1106
    発行日: 1959/08/25
    公開日: 2010/02/19
    ジャーナル フリー
    Systematic examinations were made on the alkaloids of Veratrum grandiflorum (MAXIM.) LOESENER FIL growing in Hokkaido. As the free bases, jervine (yield, 0.2%), veratramine, and rubijervine were isolated and identified. The so-called amorphous base was found to contain a few kinds of unknown ester-alkaloids, as evidenced by paper chromatography, and these were separated by chromatopile. The main alkaloid was obtained in 0.01% yield as a substance (Ea) of C32H47O8N⋅H2O, m.p. 235°(decomp.), [α]D15 -10.9°(c=1.65, CHCl3); UV λmaxEtOH 217mμ (log ε 3.00); IR maxNujol 5.82, 6.02μ. Examination of the hydrolyzate of (Ea) showed it to be the zygadenine δ-lactone monoester of angelic acid.
  • コウシュウウヤクのアルカロイド (補遺15) dl-7-Methylcoclaurineの合成
    山口 秀夫, 中野 欣一
    1959 年 79 巻 8 号 p. 1106-1107
    発行日: 1959/08/25
    公開日: 2010/02/19
    ジャーナル フリー
    As one of the compounds allied to coclaurine (I), dl-7-methylcoclaurine (XII), not yet reported in any literature, was synthesized.
  • トウオガタマMichelia fuscata BLUMEのアルカロイド その2
    伊藤 一男, 内田 郁子
    1959 年 79 巻 8 号 p. 1108-1111
    発行日: 1959/08/25
    公開日: 2010/02/19
    ジャーナル フリー
    Examinations were made for the presence of quaternary bases in the leaves, and tertiary and quaternary bases in the trunk bark of Michelia fuscata BLUME (synonym Magnolia fuscata ANDR. (Japanese name ‘Toh-ogatama’) (Magnoliaceae family)). Magnolamine (I) was obtained as the tertiary base from both portions, and magnocurarine (II) and magnoflorine (III) were identified as the quaternary bases. Content of tertiary and quaternary bases in the leaves and trunk bark of this plant is listed in Table I.
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